U.S. patent number 6,582,837 [Application Number 09/112,364] was granted by the patent office on 2003-06-24 for organic electroluminescence device.
This patent grant is currently assigned to NEC Corporation. Invention is credited to Hitoshi Ishikawa, Atushi Oda, Satoru Toguchi.
United States Patent |
6,582,837 |
Toguchi , et al. |
June 24, 2003 |
Organic electroluminescence device
Abstract
An organic electroluminescence device having one or more organic
thin layers including a luminescent layer between an anode and a
cathode, wherein at least one of the organic thin layers contains a
compound or compounds selected from the group consisting of
particular bianthryl, binaphthyl, trianthrylene and
naphthylanthracene compounds, alone or in combination, the general
formula of bianthryl compound being shown as follows: ##STR1##
Inventors: |
Toguchi; Satoru (Tokyo,
JP), Oda; Atushi (Tokyo, JP), Ishikawa;
Hitoshi (Tokyo, JP) |
Assignee: |
NEC Corporation (Tokyo,
JP)
|
Family
ID: |
27459162 |
Appl.
No.: |
09/112,364 |
Filed: |
July 9, 1998 |
Foreign Application Priority Data
|
|
|
|
|
Jul 14, 1997 [JP] |
|
|
9-188639 |
Nov 20, 1997 [JP] |
|
|
9-319430 |
Feb 12, 1998 [JP] |
|
|
10-029996 |
Apr 15, 1998 [JP] |
|
|
10-104564 |
|
Current U.S.
Class: |
428/690; 313/504;
313/506; 428/917 |
Current CPC
Class: |
H01L
51/0058 (20130101); H01L 51/006 (20130101); H01L
51/0059 (20130101); H01L 51/0067 (20130101); H01L
51/007 (20130101); H01L 51/0079 (20130101); H01L
51/0081 (20130101); H01L 51/5012 (20130101); H01L
51/5048 (20130101); Y10S 428/917 (20130101) |
Current International
Class: |
H01L
51/30 (20060101); H01L 51/05 (20060101); H01L
51/50 (20060101); H05B 033/12 () |
Field of
Search: |
;428/690,917
;313/504,506 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
54-71090 |
|
Jun 1979 |
|
JP |
|
62-76576 |
|
Apr 1987 |
|
JP |
|
5-94875 |
|
Apr 1993 |
|
JP |
|
7-138561 |
|
May 1995 |
|
JP |
|
7-224012 |
|
Aug 1995 |
|
JP |
|
8-12600 |
|
Jan 1996 |
|
JP |
|
8-20771 |
|
Jan 1996 |
|
JP |
|
8-40997 |
|
Feb 1996 |
|
JP |
|
8-53397 |
|
Feb 1996 |
|
JP |
|
8-87122 |
|
Apr 1996 |
|
JP |
|
8-239655 |
|
Sep 1996 |
|
JP |
|
8-239656 |
|
Sep 1996 |
|
JP |
|
8-245643 |
|
Sep 1996 |
|
JP |
|
8-269133 |
|
Oct 1996 |
|
JP |
|
8-333569 |
|
Dec 1996 |
|
JP |
|
11-111458 |
|
Apr 1999 |
|
JP |
|
11-111460 |
|
Apr 1999 |
|
JP |
|
3008917 |
|
Dec 1999 |
|
JP |
|
Other References
English language translation of JP 8-333569 (Dec. 1996)..
|
Primary Examiner: Yamnitzky; Marie
Attorney, Agent or Firm: Young & Thompson
Claims
What is claimed is:
1. An organic electroluminescence device having one or more organic
thin layers including a luminescent layer between an anode and a
cathode, wherein at least one of the organic thin layers contains
at least one of compounds selected from the group consisting of the
compounds represented by general formulas I, II, III, and IV, alone
or in combination; ##STR23##
wherein R.sub.1.sup.1 to R.sub.1.sup.18 independently represent
hydrogen, halogen, hydroxy, a substituted or unsubstituted amino,
nitro, cyano, a substituted or unsubstituted alkyl, a substituted
or unsubstituted alkenyl, a substituted or unsubstituted
cycloalkyl, a substituted or unsubstituted alkoxy, a substituted or
unsubstituted aromatic hydrocarbon, a substituted or unsubstituted
aromatic heterocycle, a substituted or unsubstituted aralkyl, a
substituted or unsubstituted aryloxy, a substituted or
unsubstituted alkoxycarbonyl, or carboxyl groups; or two of
R.sub.1.sup.1 to R.sub.1.sup.9 or two of R.sub.1.sup.10 to
R.sub.1.sup.18 may be combined together to form a ring, although at
least one of R.sub.1.sup.1 to R.sub.1.sup.18 is a diarylamino group
represented by --NAr.sub.1.sup.1 Ar.sub.1.sup.2 wherein
Ar.sub.1.sup.1 and Ar.sub.1.sup.2 independently represent a
substituted or unsubstituted aryl group having 6 to 20 carbon
atoms; ##STR24##
wherein R.sub.2.sup.1 to R.sub.2.sup.14 independently represent
hydrogen, a halogen, hydroxy, a substituted or unsubstituted amino,
nitro, cyano, a substituted or unsubstituted alkyl, a substituted
or unsubstituted alkenyl, a substituted or unsubstituted
cycloalkyl, a substituted or unsubstituted alkoxy, a substituted or
unsubstituted aromatic hydrocarbon, a substituted or unsubstituted
aromatic heterocycle, a substituted or unsubstituted aralkyl, a
substituted or unsubstituted aryloxy, a substituted or
unsubstituted alkoxycarbonyl, or carboxyl groups; or two of
R.sub.2.sup.1 to R.sub.2.sup.7, or R.sub.2.sup.8 to R.sub.2.sup.14
may form a ring, although at least one of R.sub.2.sup.1 to
R.sub.2.sup.14 is a diarylamino group represented by
--NAr.sub.2.sup.1 Ar.sub.2.sup.2 wherein Ar.sub.2.sup.1 is a
substituted aryl group having 6 to 20 carbon atoms which has at
least one substituted or unsubstituted styryl substituent and
Ar.sub.2.sup.2 is a substituted or unsubstituted aryl group having
6 to 20 carbon atoms; ##STR25##
wherein R.sub.3.sup.1 to R.sub.3.sup.26 independently represent
hydrogen, a halogen, hydroxy, a substituted or unsubstituted amino,
nitro, cyano, a substituted or unsubstituted alkyl, a substituted
or unsubstituted alkenyl, a substituted or unsubstituted
cycloalkyl, a substituted or unsubstituted alkoxy, a substituted or
unsubstituted aromatic hydrocarbon, a substituted or unsubstituted
aromatic heterocycle, a substituted or unsubstituted aralkyl, a
substituted or unsubstituted aryloxy, a substituted or
unsubstituted alkoxycarbonyl, or carboxyl groups; or two of
R.sub.3.sup.1 to R.sub.3.sup.9, or two of R.sub.3.sup.10 to
R.sub.3.sup.13 and two of R.sub.3.sup.23 to R.sub.3.sup.26, or two
of R.sub.3.sup.14 to R.sub.3.sup.22 may form a ring, although at
least one of R.sub.3.sup.1 to R.sub.3.sup.26 is a diarylamino group
represented by --NAr.sub.3.sup.1 Ar.sub.3.sup.2 wherein
Ar.sub.3.sup.1 and Ar.sub.3.sup.2 are independently a substituted
or unsubstituted aryl group having 6 to 20 carbon atoms;
##STR26##
wherein R.sub.4.sup.1 to R.sub.4.sup.16 independently represent
hydrogen, a halogen, hydroxy, a substituted or unsubstituted amino,
nitro, cyano, a substituted or unsubstituted alkyl, a substituted
or unsubstituted alkenyl, a substituted or unsubstituted
cycloalkyl, a substituted or unsubstituted alkoxy, a substituted or
unsubstituted aromatic hydrocarbon, a substituted or unsubstituted
aromatic heterocycle, a substituted or unsubstituted aralkyl, a
substituted or unsubstituted aryloxy, a substituted or
unsubstituted alkoxycarbonyl, or carboxyl groups; or two of
R.sub.4.sup.1 to R.sub.4.sup.9, or R.sub.4.sup.10 to R.sub.4.sup.16
may form a ring, although at least one of R.sub.4.sup.1 to
R.sub.4.sup.16 is a diarylamino group represented by
--NAr.sub.4.sup.1 Ar.sub.4.sup.2 wherein Ar.sub.4.sup.1 and
Ar.sub.4.sup.2 are independently a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms.
2. An organic electroluminescence device as claimed in claim 1,
wherein the compound is a bianthryl compound represented by general
formula I.
3. An organic electroluminescence device as claimed in claim 1,
wherein the compound is a naphthyl compound represented by general
formula II.
4. An organic electroluminescence device as claimed in claim 1,
wherein the compound is a trianthrylene compound represented by
general formula III.
5. An organic electroluminescence device as claimed in claim 1,
wherein the compound is a naphthylanthracene compound represented
by general formula IV.
6. An organic electroluminescence device as claimed in claim 1,
wherein the at least one of the organic thin layers is a
hole-transporting layer.
7. An organic electroluminescence device as claimed in claim 1,
wherein the at least one of the organic thin layers is an
electron-transporting layer.
8. An organic electroluminescence device as claimed in claim 1,
wherein the at least one of the organic thin layers is the
luminescent layer.
9. An organic electroluminescence device as claimed in claim 1,
wherein the at least one compound is represented by general formula
I, and at least one of Ar.sub.1.sup.1 and Ar.sub.1.sup.2 in
--NAr.sub.1.sup.1 Ar.sub.1.sup.2 group has one substituted or
unsubstituted styryl group as a substitutent.
10. An organic electroluminescence device as claimed in claim 1,
wherein the at least one compound is represented by general formula
III, and at least one of Ar.sub.3.sup.1 and Ar.sub.3.sup.2 in
--NAr.sub.3.sup.1 Ar.sub.3.sup.2 group has one substituted or
unsubstituted styryl group as a substituent.
11. An organic electroluminescence device as claimed in claim 1,
wherein the at least one compound is represented by the general
formula IV, and at least one of Ar.sub.4.sup.1 and Ar.sub.4.sup.2
in --NAr.sub.4.sup.1 Ar.sub.4.sup.2 group has one substituted or
unsubstituted styryl group as a substitutent.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an electroluminescence(EL) device with
excellent luminescence properties.
2. Description of the Related Art
An organic electroluminescence device is a self-light emitting
device utilizing the principle that applying an electric field to a
fluorescent substance causes its light emission through
recombination energy of positive holes injected from an anode and
electrons from a cathode. Since C. W. Tang et al reported an
organic EL device of a layered type driven by a low voltage (C. W.
Tang, S. A. VanSlyke, Applied Physics Letters, Vol.51, 913(1987)),
an organic EL device composed of organic materials has been
intensively investigated. Tang et al. has used
tris(8-hydroxyquinoline) aluminum in a luminescent layer and a
triphenyl diamine derivative in a hole-transporting layer. A
layered structure has advantages such as an improved efficiency of
injecting positive holes into a luminescent layer; an improved
efficiency of generating excitons obtained from carrier
recombination, by blocking electrons injected from a cathode; and
confinement of excitons generated in a luminescent layer. As is
shown above, well-known structures for an organic EL device include
a two-layer type comprising a hole-transporting(injection) layer
and an electron-transporting luminescent layer, and a three-layer
type comprising a hole-transporting(injection) layer, a luminescent
layer and an electron-transporting (injection) layer. In these
layered structures of devices, various device structures and
manufacturing processes have been devised for improving an
efficiency of recombination of injected positive holes and
electrons.
Conventionally known light emission materials are chelate complexes
such as tris(8-hydroxyquinoline) aluminum complex, coumarin
derivatives, tetraphenylbutadiene derivatives, bisstyryl arylenes
and oxadiazole derivatives. It has been reported that they may give
a luminescent color in the visible region from blue to red, and
thus they are promising for realizing a color-display device(e.g.,
JP-A 8-239655, JP-A 7-138561 and JP-A 3-200889).
Electron-transporting materials are well-known e.g., oxadiazole
derivatives and triazole derivatives.
Hole-transporting materials are well-known, e.g., triphenylamines
and aromatic diamines such as
4,4',4"-tris(3-methylphenylphenylamino)triphenylamine, which is a
star-burst molecule, and
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine
(e.g., JP-A 8-20771, JP-A 8-40995, JP-A 8-40997, JP-A 8-53397, JP-A
8-87122). Recently, 3,3'-diamino-1,1'-binaphtyl derivatives have
been disclosed in JP-A 9-255948. It has been described that the
above compound has a higher glass-transition temperature, and thus,
when used as a hole-transporting material, may give an organic EL
device highly reliable under a drive condition of a high current
density. There is, however, a problem of a low luminance.
SUMMARY OF THE INVENTION
There have been recently disclosed or reported organic EL devices
with a high luminance and a long life, which are, however, not
necessarily satisfactory. It has been, therefore, desired to
develop materials exhibiting a high performance. Thus, an objective
of this invention is to provide an organic EL device with an
improved luminance.
We have intensely investigated for solving the above problems, and
have obtained the following observations on an organic EL device
prepared by using at least one of the compounds selected from the
group consisting of; (1) particular bianthryl compounds[I], (2)
particular binaphthyl compounds[II], (3) particular trianthrylene
compounds[III], and (4 ) particular naphthylanthracene
compounds[IV] as a luminescent material, leading to this
invention.
1. An organic EL device prepared by using the particular bianthryl
compound[I] can exhibit a higher-luminance luminescence than a
conventional one. The material has a good carrier transport
property. An organic EL device prepared by using the material as a
hole- or electron-transporting material, or by using a mixture
layer of the above material and another hole- or
electron-transporting material, may exhibit a higher-luminance
luminescence than a conventional one. An organic EL device may give
a particularly high-luminance luminescence, when employing the
above bianthryl compound substituted with a diarylamino group as a
luminescent, hole-transporting or electron-transporting material.
An organic EL device may give a particularly high-luminance
luminescence, when employing the above bianthryl compound whose
aryl group is substituted with a styryl group, as a luminescent,
hole-transporting or electron-transporting material.
2. A luminance of an organic EL device may be improved by using the
particular binaphthyl compound[II] in a hole-transporting layer. In
addition, an organic EL is provided, in which the binaphthyl
compound is used as a luminescent material and/or an
electron-transporting material.
3. An organic EL device prepared by using the particular
trianthrylene compound[III] can exhibit a higher-luminance
luminescence than a conventional one. The material has a good
carrier transport property. An organic EL device may exhibit a
higher-luminance luminescence than a conventional one, by forming a
hole- or electron-transporting layer made of the material or of a
mixture of the material and another hole- or electron-transporting
material.
An organic EL device may give a particularly high-luminance
luminescence, when employing the above trianthrylene compound
substituted with a diarylamino group as a luminescent,
hole-transporting or electron-transporting material. An organic EL
device may give a particularly high-luminance luminescence, when
employing the above trianthrylene compound whose aryl group is
substituted with a styryl group, as a luminescent,
hole-transporting or electron-transporting material.
4. An organic EL device prepared by using the particular
naphthylanthracene compound[IV] can exhibit a higher-luminance
luminescence than a conventional one. The material has a good
carrier transport property. An organic EL device may exhibit a
higher-luminance luminescence than a conventional one, by forming a
hole- or electron-transporting layer made of the material or of a
mixture of the material and another hole- or electron-transporting
material.
An organic EL device may give a particularly high-luminance
luminescence, when employing the above naphthylanthracene compound
substituted with a diarylamino group as a luminescent,
hole-transporting or electron-transporting material. An organic EL
device may give a particularly high-luminance luminescence, when
employing the above naphthylanthracene compound whose aryl group is
substituted with a styryl group, as a luminescent,
hole-transporting or electron-transporting material.
An organic EL device according to this invention which employs a
compound or compounds selected from the group consisting of the
above four types of compounds, can exhibit a higher-luminance
luminescence than a conventional one, indicating that this
invention is highly effective.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 4 are cross-sections of examples of an organic EL device
according to this invention, wherein 1 is a substrate, 2 is an
anode, 3 is a hole-transporting layer, 4 is a luminescent layer, 5
is an electron-transporting layer and 6 is a cathode.
DETAILED DESCRIPTION OF THE INVENTION
(1) The above particular bianthryl compounds are represented by the
general formula [I]-(1); ##STR2## wherein R.sub.1.sup.1 to
R.sub.1.sup.18 independently represent hydrogen, halogen, hydroxy,
a substituted or unsubstituted amino, nitro, cyano, a substituted
or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a
substituted or unsubstituted cycloalkyl, a substituted or
unsubstituted alkoxy, a substituted or unsubstituted aromatic
hydrocarbon, a substituted or unsubstituted aromatic heterocycle, a
substituted or unsubstituted aralkyl, a substituted or
unsubstituted aryloxy, a substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.1.sup.1 to
R.sub.1.sup.18 may be combined together to form a ring; or [I]-(2)
##STR3## wherein R.sub.1.sup.1 to R.sub.1.sup.18 independently
represent hydrogen, halogen, hydroxy, a substituted or
unsubstituted amino, nitro, cyano, a substituted or unsubstituted
alkyl, a substituted or unsubstituted alkenyl, a substituted or
unsubstituted cycloalkyl, a substituted or unsubstituted alkoxy, a
substituted or unsubstituted aromatic hydrocarbon, a substituted or
unsubstituted aromatic heterocycle, a substituted or unsubstituted
aralkyl, a substituted or unsubstituted aryloxy, a substituted or
unsubstituted alkoxycarbonyl, or carboxyl groups; or two of
R.sub.1.sup.1 to R.sub.1.sup.18 may be combined together to form a
ring, although at least one of R.sub.1.sup.1 to R.sub.1.sup.18 is a
diarylamino group represented by --NAr.sub.1.sup.1 Ar.sub.1.sup.2
wherein Ar.sub.1.sup.1 and Ar.sub.1.sup.2 independently represent a
substituted or unsubstituted aryl group having 6 to 20 carbon
atoms.
In the above R.sub.1.sup.1 to R.sub.1.sup.18, the halogen atom may
be fluorine, chlorine, bromine or iodine.
The substituted or unsubstituted amino group may be represented by
--NX.sup.1 X.sup.2, wherein X.sup.1 and X.sup.2 may be
independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl,
s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl,
1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3-dihydroxy-t-butyl,
1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl,
2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl,
2,3-dichloro-t-butyl, 1,2,3-trichloropropyl, bromomethyl,
1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl,
1,3-dibromoisopropyl, 2,3-dibromo-t-butyl, 1,2,3-tribromopropyl,
iodomethyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl,
1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-t-butyl,
1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl,
2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl,
2,3-diamino-t-butyl, 1,2,3-triaminopropyl, cyanomethyl,
1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl,
1,3-dicyanoisopropyl, 2,3-dicyano-t-butyl, 1,2,3-tricyanopropyl,
nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl,
1,2-dinitroethyl, 1,3-dinitroisopropyl, 2,3-dinitro-t-butyl,
1,2,3-trinitropropyl, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,
2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,
4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl,
9-naphthacenyl, 4-styrylphenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl,
2-biphenylyl, 3-biphenylyl, 4-biphenylyl, p-terphenyl-4-yl,
p-terphenyl-3-yl, p-terphenyl-2-yl,m-terphenyl-4-yl,
m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl,
p-t-butylphenyl, p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl,
4-methyl-1-naphthyl, 4-methyl-1-anthryl, 4'-methylbiphenylyl,
4"-t-butyl-p-terphenyl-4-yl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl,
2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 2-indolyl, 3-indolyl,
4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl,
3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl,
7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl,
4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl,
1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl,
5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl,
2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl,
7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl,
4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl,
8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl,
1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl,
1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl,
4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl,
8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl,
1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl,
1,7-phenanthrolin-2-yl, 1,7-phenanthrolin-3-yl,
1,7-phenanthrolin-4-yl, 1,7-phenanthrolin-5-yl,
1,7-phenanthrolin-6-yl, 1,7-phenanthrolin-8-yl,
1,7-phenanthrolin-9-yl, 1,7-phenanthrolin-10-yl,
1,8-phenanthrolin-2-yl, 1,8-phenanthrolin-3-yl,
1,8-phenanthrolin-4-yl, 1,8-phenanthrolin-5-yl,
1,8-phenanthrolin-6-yl, 1,8-phenanthrolin-7-yl,
1,8-phenanthrolin-9-yl, 1,8-phenanthrolin-10-yl,
1,9-phenanthrolin-2-yl, 1,9-phenanthrolin-3-yl,
1,9-phenanthrolin-4-yl, 1,9-phenanthrolin-5-yl,
1,9-phenanthrolin-6-yl, 1,9-phenanthrolin-7-yl,
1,9-phenanthrolin-8-yl, 1,9-phenanthrolin-10-yl,
1,10-phenanthrolin-2-yl, 1,10-phenanthrolin-3-yl,
1,10-phenanthrolin-4-yl, 1,10-phenanthrolin-5-yl,
2,9-phenanthrolin-1-yl, 2,9-phenanthrolin-3-yl,
2,9-phenanthrolin-4-yl, 2,9-phenanthrolin-5-yl,
2,9-phenanthrolin-6-yl, 2,9-phenanthrolin-7-yl,
2,9-phenanthrolin-8-yl, 2,9-phenanthrolin-10-yl,
2,8-phenanthrolin-1-yl, 2,8-phenanthrolin-3-yl,
2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl,
2,8-phenanthrolin-6-yl, 2,8-phenanthrolin-7-yl,
2,8-phenanthrolin-9-yl, 2,8-phenanthrolin-10-yl,
2,7-phenanthrolin-1-yl, 2,7-phenanthrolin-3-yl,
2,7-phenanthrolin-4-yl, 2,7-phenanthrolin-5-yl,
2,7-phenanthrolin-6-yl, 2,7-phenanthrolin-8-yl,
2,7-phenanthrolin-9-yl, 2,7-phenanthrolin-10-yl, 1-phenazinyl,
2-phenazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl,
4-phenothiazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl,
4-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl,
5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl,
2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl,
2-methylpyrrol-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl,
3-methylpyrrol-4-yl, 3-methylpyrrol-5-yl, 2-t-butylpyrrol-4-yl,
3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl,
4-methyl-1-indolyl, 2-methyl-3-indolyl, 4-methyl-3-indolyl,
2-t-butyl-1-indolyl, 4-t-butyl-1-indolyl, 2-t-butyl-3-indolyl or
4-t-butyl-3-indolyl.
The substituted or unsubstituted alkyl group may be methyl, ethyl,
propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl,
n-hexyl, n-heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl,
2-hydroxyethyl, 2-hydroxyisobutyl, 1,2-dihydroxyethyl,
1,3-dihydroxyisopropyl, 2,3-dihydroxy-t-butyl,
1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl,
2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl,
2,3-dichloro-t-butyl, 1,2,3-trichloropropyl, bromomethyl,
1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl,
1,3-dibromoisopropyl, 2,3-dibromo-t-butyl, 1,2,3-tribromopropyl,
iodomethyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl,
1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-t-butyl,
1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl,
2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl,
2,3-diamino-t-butyl, 1,2,3-triaminopropyl, cyanomethyl,
1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl,
1,3-dicyanoisopropyl, 2,3-dicyano-t-butyl, 1,2,3-tricyanopropyl,
nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl,
1,2-dinitroethyl, 1,3-dinitroisopropyl, 2,3-dinitro-t-butyl or
1,2,3-trinitropropyl.
The substituted or unsubstituted alkenyl group may be vinyl, allyl,
1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl,
styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl,
1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl,
3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl,
1-phenyl-1-butenyl or 3-phenyl-1-butenyl.
The substituted or unsubstituted alkenyl group may be cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl and 4-methylcyclohexyl.
The substituted or unsubstituted alkoxy group is represented by
--OY, wherein Y may be ethyl, propyl, isopropyl, n-butyl, s-butyl,
isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl,
1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3-dihydroxy-t-butyl,
1,2,3-trihydroxypropyl, chloromethyl, 1-chloroethyl, 2-chloroethyl,
2-chloroisobutyl, 1,2-dichloroethyl, 1,3-dichloroisopropyl,
2,3-dichloro-t-butyl, 1,2,3-trichloropropyl, bromomethyl,
1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl,
1,3-dibromoisopropyl, 2,3-dibromo-t-butyl, 1,2,3-tribromopropyl,
iodomethyl, 1-iodoethyl, 2-iodoethyl, 2-iodoisobutyl,
1,2-diiodoethyl, 1,3-diiodoisopropyl, 2,3-diiodo-t-butyl,
1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl, 2-aminoethyl,
2-aminoisobutyl, 1,2-diaminoethyl, 1,3-diaminoisopropyl,
2,3-diamino-t-butyl, 1,2,3-triaminopropyl, cyanomethyl,
1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl, 1,2-dicyanoethyl,
1,3-dicyanoisopropyl, 2,3-dicyano-t-butyl, 1,2,3-tricyanopropyl,
nitromethyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl,
1,2-dinitroethyl, 1,3-dinitroisopropyl, 2,3-dinitro-t-butyl or
1,2,3-trinitropropyl.
The substituted or unsubstituted aromatic hydrocarbon group may be
phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl,
1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl,
9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl,
1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenylyl, 3-biphenylyl,
4-biphenylyl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl,
m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl,
m-tolyl, p-tolyl, p-t-butylphenyl, p-(2-phenylpropyl)phenyl,
3-methyl-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-1-anthryl,
4'-methylbiphenylyl or 4"-t-butyl-p-terphenyl-4-yl.
The substituted or unsubstituted aromatic heterocyclic group may be
1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridinyl,
3-pyridinyl, 4-pyridinyl, 1-indolyl, 2-indolyl, 3-indolyl,
4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl,
2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl,
6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuranyl,
3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl,
7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl,
4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl,
7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl,
6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl,
4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl,
8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl,
1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl,
9-carbazolyl, 1-phenanthridinyl, 2-phenanthridinyl,
3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl,
7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl,
10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl,
4-acridinyl, 9-acridinyl, 1,7-phenanthrolin-2-yl,
1,7-phenanthrolin-3-yl, 1,7-phenanthrolin-4-yl,
1,7-phenanthrolin-5-yl, 1,7-phenanthrolin-6-yl,
1,7-phenanthrolin-8-yl, 1,7-phenanthrolin-9-yl,
1,7-phenanthrolin-10-yl, 1,8-phenanthrolin-2-yl,
1,8-phenanthrolin-3-yl, 1,8-phenanthrolin-4-yl,
1,8-phenanthrolin-5-yl, 1,8-phenanthrolin-6-yl,
1,8-phenanthrolin-7-yl, 1,8-phenanthrolin-9-yl,
1,8-phenanthrolin-10-yl, 1,9-phenanthrolin-2-yl,
1,9-phenanthrolin-3-yl, 1,9-phenanthrolin-4-yl,
1,9-phenanthrolin-5-yl, 1,9-phenanthrolin-6-yl,
1,9-phenanthrolin-7-yl, 1,9-phenanthrolin-8-yl,
1,9-phenanthrolin-10-yl, 1,10-phenanthrolin-2-yl,
1,10-phenanthrolin-3-yl, 1,10-phenanthrolin-4-yl,
1,10-phenanthrolin-5-yl, 2,9-phenanthrolin-1-yl,
2,9-phenanthrolin-3-yl, 2,9-phenanthrolin-4-yl,
2,9-phenanthrolin-5-yl, 2,9-phenanthrolin-6-yl,
2,9-phenanthrolin-7-yl, 2,9-phenanthrolin-8-yl,
2,9-phenanthrolin-10-yl, 2,8-phenanthrolin-1-yl,
2,8-phenanthrolin-3-yl, 2,8-phenanthrolin-4-yl,
2,8-phenanthrolin-5-yl, 2,8-phenanthrolin-6-yl,
2,8-phenanthrolin-7-yl, 2,8-phenanthrolin-9-yl,
2,8-phenanthrolin-10-yl, 2,7-phenanthrolin-1-yl,
2,7-phenanthrolin-3-yl, 2,7-phenanthrolin-4-yl,
2,7-phenanthrolin-5-yl, 2,7-phenanthrolin-6-yl,
2,7-phenanthrolin-8-yl, 2,7-phenanthrolin-9-yl,
2,7-phenanthrolin-10-yl, 1-phenazinyl, 2- phenazinyl,
1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl,
4-phenothiazinyl, 10-phenothiazinyl, 1-phenoxazinyl,
2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl,
2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl,
3-furazanyl, 2-thienyl, 3-thienyl, 2-methylpyrrol-1-yl,
2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl, 2-methylpyrrol-5-yl,
3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl,
3-methylpyrrol-5-yl, 2-t-butylpyrrol-4-yl,
3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl,
4-methyl-1-indolyl, 2-methyl-3-indolyl, 4-methyl-3-indolyl,
2-t-butyl-1-indolyl, 4-t-butyl-1-indolyl, 2-t-butyl-3-indolyl or
4-t-butyl-3-indolyl.
The substituted or unsubstituted aralkyl group may be benzyl,
1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl,
phenyl-t-butyl, .alpha.-naphthylmethyl, 1-.alpha.-naphthylethyl,
2-.alpha.-naphthylethyl, 1-.alpha.-naphthylisopropyl,
2-.alpha.-naphthylisopropyl, .beta.-naphthylmethyl,
1-.beta.-naphthylethyl, 2-.beta.-naphthylethyl,
1-.beta.-naphthylisopropyl, 2-.beta.-naphthylisopropyl,
1-pyrrolylmethyl, 2-(1-pyrrolyl)ethyl, p-methylbenzyl,
m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl,
o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl,
p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl,
m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl,
o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl,
p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl,
1-hydoxy-2-phenylisopropyl or 1-chloro-2-phenylisopropyl.
The substituted or unsubstituted aryloxy group is represented by
--OZ, wherein Z may be phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,
2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,
4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl,
9-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenylyl,
3-biphenylyl, 4-biphenylyl, p-terphenyl-4-yl, p-terphenyl-3-yl,
p-terphenyl-2-yl,m-terphenyl-4-yl, m-terphenyl-3-yl,
m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-t-butylphenyl,
p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl,
4-methyl-1-anthryl, 4'-methylbiphenylyl,
4"-t-butyl-p-terphenyl-4-yl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl,
2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 2-indolyl, 3-indolyl,
4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl,
3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl,
7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl,
4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl,
1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl,
5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl,
2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl,
7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl,
4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl,
8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl,
1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl,
1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl,
4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl,
8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl,
1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl,
1,7-phenanthrolin-2-yl, 1,7-phenanthrolin-3-yl,
1,7-phenanthrolin-4-yl, 1,7-phenanthrolin-5-yl,
1,7-phenanthrolin-6-yl, 1,7-phenanthrolin-8-yl,
1,7-phenanthrolin-9-yl, 1,7-phenanthrolin-10-yl,
1,8-phenanthrolin-2-yl, 1,8-phenanthrolin-3-yl,
1,8-phenanthrolin-4-yl, 1,8-phenanthrolin-5-yl,
1,8-phenanthrolin-6-yl, 1,8-phenanthrolin-7-yl,
1,8-phenanthrolin-9-yl, 1,8-phenanthrolin-10-yl,
1,9-phenanthrolin-2-yl, 1,9-phenanthrolin-3-yl,
1,9-phenanthrolin-4-yl, 1,9-phenanthrolin-5-yl,
1,9-phenanthrolin-6-yl, 1,9-phenanthrolin-7-yl,
1,9-phenanthrolin-8-yl, 1,9-phenanthrolin-10-yl,
1,10-phenanthrolin-2-yl, 1,10-phenanthrolin-3-yl,
1,10-phenanthrolin-4-yl, 1,10-phenanthrolin-5-yl,
2,9-phenanthrolin-1-yl, 2,9-phenanthrolin-3-yl,
2,9-phenanthrolin-4-yl, 2,9-phenanthrolin-5-yl,
2,9-phenanthrolin-6-yl, 2,9-phenanthrolin-7-yl,
2,9-phenanthrolin-8-yl, 2,9-phenanthrolin-10-yl,
2,8-phenanthrolin-1-yl, 2,8-phenanthrolin-3-yl,
2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl,
2,8-phenanthrolin-6-yl, 2,8-phenanthrolin-7-yl,
2,8-phenanthrolin-9-yl, 2,8-phenanthrolin-10-yl,
2,7-phenanthrolin-1-yl, 2,7-phenanthrolin-3-yl,
2,7-phenanthrolin-4-yl, 2,7-phenanthrolin-5-yl,
2,7-phenanthrolin-6-yl, 2,7-phenanthrolin-8-yl,
2,7-phenanthrolin-9-yl, 2,7-phenanthrolin-10-yl, 1-phenazinyl,
2-phenazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl,
4-phenothiazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl,
4-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl,
5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl,
2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl,
2-methylpyrrol-5-yl, 3-methylpyrrol-1-yl, 3-methylpyrrol-2-yl,
3-methylpyrrol-4-yl, 3-methylpyrrol-5-yl, 2-t-butylpyrrol-4-yl,
3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl,
4-methyl-1-indolyl, 2-methyl-3-indolyl, 4-methyl-3-indolyl,
2-t-butyl-1-indolyl, 4-t-butyl-1-indolyl, 2-t-butyl-3-indolyl or
4-t-butyl-3-indolyl.
The substituted or unsubstituted alkoxycarbonyl group is
represented by --COOY', wherein Y' may be methyl, ethyl, propyl,
isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl,
2-hydroxyisobutyl, 1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl,
2,3-dihydroxy-t-butyl, 1,2,3-trihydroxypropyl, chloromethyl,
1-chloroethyl, 2-chloroethyl, 2-chloroisobutyl, 1,2-dichloroethyl,
1,3-dichloroisopropyl, 2,3-dichloro-t-butyl, 1,2,3-trichloropropyl,
bromomethyl, 1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl,
1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3-dibromo-t-butyl,
1,2,3-tribromopropyl, iodomethyl, 1-iodoethyl, 2-iodoethyl,
2-iodoisobutyl, 1,2-diiodoethyl, 1,3-diiodoisopropyl,
2,3-diiodo-t-butyl, 1,2,3-triiodopropyl, aminomethyl, 1-aminoethyl,
2-aminoethyl, 2-aminoisobutyl, 1,2-diaminoethyl,
1,3-diaminoisopropyl, 2,3-diamino-t-butyl, 1,2,3-triaminopropyl,
cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 2-cyanoisobutyl,
1,2-dicyanoethyl, 1,3-dicyanoisopropyl, 2,3-dicyano-t-butyl,
1,2,3-tricyanopropyl, nitromethyl, 1-nitroethyl, 2-nitroethyl,
2-nitroisobutyl, 1,2-dinitroethyl, 1,3-dinitroisopropyl,
2,3-dinitro-t-butyl or 1,2,3-trinitropropyl.
Bivalent groups which may form a ring include tetramethylene,
pentamethylene, hexamethylene, diphenylmethan-2,2'-diyl,
diphenylethan-3,3'-diyl and diphenylpropan-4,4'-diyl.
Preferable compounds for this invention are those represented by
formula [I]-(2), wherein at least one of R.sub.1.sup.1 to
R.sub.1.sup.18 is --NAr.sub.1.sup.1 Ar.sub.1.sup.2 wherein
Ar.sub.1.sup.1 and Ar.sub.1.sup.2 independently represent a
substituted or unsubstituted aryl group having 6 to 20 carbon
atoms; and the remaining groups among R.sub.1.sup.1 to
R.sub.1.sup.18 independently represent hydrogen, halogen, hydroxy,
the above substituted or unsubstituted amino, nitro, cyano, the
above substituted or unsubstituted alkyl, the above substituted or
unsubstituted alkenyl, the above substituted or unsubstituted
cycloalkyl, the above substituted or unsubstituted alkoxy, the
above substituted or unsubstituted aromatic hydrocarbon, the above
substituted or unsubstituted aromatic heterocycle, the above
substituted or unsubstituted aralkyl, the above substituted or
unsubstituted aryloxy, the above substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.1.sup.1 to
R.sub.1.sup.18 may be combined together to form a ring. The aryl
group having 6 to 20 carbon atoms may be phenyl, naphthyl, anthryl,
phenanthryl, naphthacenyl or pyrenyl. These aryl groups may be
substituted with a halogen, hydroxy, the above substituted or
unsubstituted amino, nitro, cyano, the above substituted or
unsubstituted alkyl, the above substituted or unsubstituted
alkenyl, the above substituted or unsubstituted cycloalkyl, the
above substituted or unsubstituted alkoxy, the above substituted or
unsubstituted aromatic hydrocarbon, the above substituted or
unsubstituted aromatic heterocycle, the above substituted or
unsubstituted aralkyl, the above substituted or unsubstituted
aryloxy, the above substituted or unsubstituted alkoxycarbonyl, or
carboxyl groups.
The styryl group which Ar.sub.1.sup.1 and Ar.sub.1.sup.2 may have
as a substituent group, may be selected from unsubstituted styryl,
2,2-diphenylvinyl, as well as substituted styryl and
2,2-diphenylvinyl groups whose terminal phenyl has substituent
groups such as a halogen, hydroxy, the above substituted or
unsubstituted amino, nitro, cyano, the above substituted or
unsubstituted alkyl, the above substituted or unsubstituted
alkenyl, the above substituted or unsubstituted cycloalkyl, the
above substituted or unsubstituted alkoxy, the above substituted or
unsubstituted aromatic hydrocarbon, the above substituted or
unsubstituted aromatic heterocycle, the above substituted or
unsubstituted aralkyl, the above substituted or unsubstituted
aryloxy, the above substituted or unsubstituted alkoxycarbonyl and
carboxyl groups.
Examples of the compounds belonging to the above [I] of this
invention will be shown below, to which this invention is not
limited. ##STR4##
(2) The above particular binaphthyl compound [II] may be
represented by general formula [II]-(1); ##STR5## wherein
R.sub.2.sup.1 to R.sub.2.sup.14 independently represent hydrogen, a
halogen, hydroxy, a substituted or unsubstituted amino, nitro,
cyano, a substituted or unsubstituted alkyl, a substituted or
unsubstituted alkenyl, a substituted or unsubstituted cycloalkyl, a
substituted or unsubstituted alkoxy, a substituted or unsubstituted
aromatic hydrocarbon, a substituted or unsubstituted aromatic
heterocycle, a substituted or to unsubstituted aralkyl, a
substituted or unsubstituted aryloxy, a substituted or
unsubstituted alkoxycarbonyl, or carboxyl groups; or two of
R.sub.2.sup.1 to R.sub.2.sup.7 and/or two of R.sub.2.sup.8 to
R.sub.2.sup.14 may form a ring; or [II]-(2); ##STR6## wherein
R.sub.2.sup.1 to R.sub.2.sup.14 independently represent hydrogen, a
halogen, hydroxy, a substituted or unsubstituted amino, nitro,
cyano, a substituted or unsubstituted alkyl, a substituted or
unsubstituted alkenyl, a substituted or unsubstituted cycloalkyl, a
substituted or unsubstituted alkoxy, a substituted or unsubstituted
aromatic hydrocarbon, a substituted or unsubstituted aromatic
heterocycle, a substituted or unsubstituted aralkyl, a substituted
or unsubstituted aryloxy, a substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.2.sup.1 to
R.sub.2.sup.7 and/or two of R.sub.2.sup.8 to R.sub.2.sup.14 may
form a ring, although at least one of R.sub.2.sup.1 to
R.sub.2.sup.14 is a diarylamino group represented by
--NAr.sub.2.sup.1 Ar.sub.2.sup.2 wherein Ar.sub.2.sup.1 is a
substituted aryl group having 6 to 20 carbon atoms which has at
least one styryl substituent and Ar.sub.2.sup.2 is a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms.
For the above R.sub.2.sup.1 to R.sub.2.sup.14, specific examples of
the halogen, the substituted or unsubstituted amino, the
substituted or unsubstituted alkyl, the substituted or
unsubstituted alkenyl, the substituted or unsubstituted cycloalkyl,
the substituted or unsubstituted alkoxy, the substituted or
unsubstituted aromatic hydrocarbon, the substituted or
unsubstituted aromatic heterocycle, the substituted or
unsubstituted aralkyl, the substituted or unsubstituted aryloxy,
and the substituted or unsubstituted alkoxycarbonyl, are as
described for the above R.sub.1.sup.1 to R.sub.1.sup.18. Examples
of the ring formed by two of R.sub.2.sup.1 to R.sub.2.sup.7 and/or
two of R.sub.2.sup.8 to R.sub.2.sup.14 ; of the substituted or
unsubstituted aryl group having 6 to 20 carbons; and of the styryl
group, are also as described for R.sub.1.sup.1 to R.sub.1.sup.18
for the compounds in [I].
Specifically, 4,4'-bis(diphenylamino)-1,1'-binaphthyl,
4,4'-bis(phenyl-p-triamino)-1,1'-binaphthyl,
4-(di-p-triamino)-1,1'-binaphthyl and
4,4'-bis(di-p-triamino)-1,1'-binaphthyl may be practically useful
examples.
More specifically, 3,3'-dimethyl-bis(diarylamino)-1,1'-binaphthyls,
especially 1,1'-binaphthyls having a styryl-substituted
diphenylamino group represented by formulas [II]-(3), [II]-(4) or
[II]-(5), are preferable and practically useful because they can
provide a high-luminance luminescent layer. This invention should
not be, however, limited to these specific examples. ##STR7##
##STR8##
The compounds in [II] may be prepared by a conventionally known
process. For example, a binaphthyl compound having a diphenylamino
group may be prepared by Ullmann reaction of an amine having a
binaphthyl structure with an aromatic halogen compound, or of a
halogen compound having a binaphthyl structure with an aromatic
amine. A styryl derivative may be prepared by well-known
Wittig-Horner reaction.
(3) The above particular trianthrylene compound [III] may be
represented by general formula [III]-(1); ##STR9## wherein
R.sub.3.sup.1 to R.sub.3.sup.26 independently represent hydrogen, a
halogen, hydroxy, a substituted or unsubstituted amino, nitro,
cyano, a substituted or unsubstituted alkyl, a substituted or
unsubstituted alkenyl, a substituted or unsubstituted cycloalkyl, a
substituted or unsubstituted alkoxy, a substituted or unsubstituted
aromatic hydrocarbon, a substituted or unsubstituted aromatic
heterocycle, a substituted or unsubstituted aralkyl, a substituted
or unsubstituted aryloxy, a substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.3.sup.1 to
R.sub.3.sup.26 may form a ring; or [III]-(2); ##STR10## wherein
R.sub.3.sup.1 to R.sub.3.sup.26 independently represent hydrogen, a
halogen, hydroxy, a substituted or unsubstituted amino, nitro,
cyano, a substituted or unsubstituted alkyl, a substituted or
unsubstituted alkenyl, a substituted or unsubstituted cycloalkyl, a
substituted or unsubstituted alkoxy, a substituted or unsubstituted
aromatic hydrocarbon, a substituted or unsubstituted aromatic
heterocycle, a substituted or unsubstituted aralkyl, a substituted
or unsubstituted aryloxy, a substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.3.sup.1 to
R.sub.3.sup.26 may form a ring, although at least one of
R.sub.3.sup.1 to R.sub.3.sup.26 is a diarylamino group represented
by --NAr.sub.3.sup.1 Ar.sub.3.sup.2 wherein Ar.sub.3.sup.1 and
Ar.sub.3.sup.2 are independently a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms, and at least one of
Ar.sub.3.sup.1 and Ar.sub.3.sup.2 has at least one styryl group as
a substituent.
For the above R.sub.3.sup.1 to R.sub.3.sup.26 specific examples of
the halogen, the substituted or unsubstituted amino, the
substituted or unsubstituted alkyl, the substituted or
unsubstituted alkenyl, the substituted or unsubstituted cycloalkyl,
the substituted or unsubstituted alkoxy, the substituted or
unsubstituted aromatic hydrocarbon, the substituted or
unsubstituted aromatic heterocycle, the substituted or
unsubstituted aralkyl, the substituted or unsubstituted aryloxy,
and the substituted or unsubstituted alkoxycarbonyl, are as
described for the above R.sub.1.sup.1 to R.sub.1.sup.18. Examples
of the ring formed by two of R.sub.3.sup.1 to R.sub.3.sup.26 ; of
the aryl group having 6 to 20 carbons; and of the styryl group, are
also as described for R.sub.1.sup.1 to R.sub.1.sup.18 for the
compounds in [I].
Examples of the compounds in [III] are, but not limited to,
[III]-(3): tri-9,10-anthrylene; [III]-(4):
10-di-p-tolylaminotri-9,10-anthrylene; [III]-(5):
10,10"-bis(di-p-tolylamino)tri-9,10-anthrylene; [III]-(6):
10-(N-phenyl-N-p-(4-methylphenylvinyl)phenylamino)tri-9,10-anthrylene;
[III]-(7):
10,10"-bis(N-phenyl-N-p-(4-methylphenylvinyl)phenylamino)tri-9,10-anthryle
ne. ##STR11##
(4) The above particular naphthylanthracene compound [IV] may be
represented by general formula ##STR12## wherein R.sub.4.sup.1 to
R.sub.4.sup.16 independently represent hydrogen, a halogen,
hydroxy, a substituted or unsubstituted amino, nitro, cyano, a
substituted or unsubstituted alkyl, a substituted or unsubstituted
alkenyl, a substituted or unsubstituted cycloalkyl, a substituted
or unsubstituted alkoxy, a substituted or unsubstituted aromatic
hydrocarbon, a substituted or unsubstituted aromatic heterocycle, a
substituted or unsubstituted aralkyl, a substituted or
unsubstituted aryloxy, a substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.4.sup.1 to
R.sub.4.sup.16 may form a ring; or [IV]-(2); ##STR13## wherein
R.sub.4.sup.1 to R.sub.4.sup.16 independently represent hydrogen, a
halogen, hydroxy, a substituted or unsubstituted amino, nitro,
cyano, a substituted or unsubstituted alkyl, a substituted or
unsubstituted alkenyl, a substituted or unsubstituted cycloalkyl, a
substituted or unsubstituted alkoxy, a substituted or unsubstituted
aromatic hydrocarbon, a substituted or unsubstituted aromatic
heterocycle, a substituted or unsubstituted aralkyl, a substituted
or unsubstituted aryloxy, a substituted or unsubstituted
alkoxycarbonyl, or carboxyl groups; or two of R.sub.4.sup.1 to
R.sub.4.sup.16 may form a ring, although at least one of
R.sub.4.sup.1 to R.sub.4.sup.16 is a diarylamino group represented
by --NAr.sub.4.sup.1 Ar.sub.4.sup.2 wherein Ar.sub.4.sup.1 and
Ar.sub.4.sup.2 are independently a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms.
In the compound represented by general formula [IV]-(2), at least
one of Ar.sub.4.sup.1 and Ar.sub.4.sup.2 preferably has at least
one styryl group as a substituent.
For the above R.sub.4.sup.1 to R.sub.4.sup.16, specific examples of
the halogen, the substituted or unsubstituted amino, the
substituted or unsubstituted alkyl, the substituted or
unsubstituted alkenyl, the substituted or unsubstituted cycloalkyl,
the substituted or unsubstituted alkoxy, the substituted or
unsubstituted aromatic hydrocarbon, the substituted or
unsubstituted aromatic heterocycle, the substituted or
unsubstituted aralkyl, the substituted or unsubstituted aryloxy,
and the substituted or unsubstituted alkoxycarbonyl, are as
described for the above R.sub.1.sup.1 to R.sub.1.sup.18. Examples
of the ring formed by two of R.sub.4.sup.1 to R.sub.4.sup.16 ; of
the aryl group having 6 to 20 carbons; and of the styryl group, are
also as described for R.sub.1.sup.1 to R.sub.1.sup.8 for the
compounds in [I].
Examples of the naphthylanthracene compounds are, but not limited
to, as follows. ##STR14##
An organic EL device according to this invention has some organic
layers between electrodes. For example, it has a structure as shown
in FIG. 1 consisting of an anode 2, a luminescent layer 4 and a
cathode 6; as shown in FIG. 2 consisting of an anode 2, a
hole-transporting layer 3, a luminescent layer 4, an
electron-transporting layer 5 and a cathode 6; as shown in FIG. 3
consisting of an anode 2, a hole-transporting layer 3, a
luminescent layer 4 and a cathode 6; or as shown in FIG. 4
consisting of an anode 2, a luminescent layer 4, an
electron-transporting layer 5 and a cathode 6. In FIGS. 1 to 4, 1
represents a substrate. The above-mentioned compounds can be
applied to any of the above organic layers, and can be added as a
dopant in another hole-transporting, luminescent or
electron-transporting material.
There is no limitation for a hole-transporting material used in
this invention, and thus any compound commonly used as a
hole-transporting material may be employed. Examples of the
hole-transporting material are
bis(di(p-tolyl)aminophenyl)-1,1-cyclohexane[01],
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine[02],
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
and star-burst type compounds (e.g., [04] to [06]). ##STR15##
##STR16##
There is no limitation for an electron-transporting material used
in this invention, and thus any compound commonly used as an
electron-transporting material may be employed. Examples of the
electron-transporting material are oxadiazoles such as
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole[07] and
bis{2-(4-t-butylphenyl)-1,3,4-oxadiazolyl}-m-phenylene[08];
triazoles such as [09] and [10]; and quinolinolic metal complexes
such as [11] to [14]. ##STR17##
An anode of an organic EL device injects positive holes into a
hole-transporting layer. It is, therefore, effective for the anode
to have a work function at least 4.5 eV. Examples of an anode
material used in this invention are indium oxide-tin alloy(ITO),
stannic oxide(NESA), gold, silver, platinum and copper. Since a
cathode injects electrons into an electron-transporting or
luminescent layer, it preferably has a lower work function.
Examples of a cathode material are, but not limited to, indium,
aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum
alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, and
magnesium-tin alloy.
Each layer of an organic EL device according to this invention may
be formed by a known process such as, but not limited to, vacuum
evaporation and spin coating. An organic thin layer used in an
organic EL device according to this invention, which contains any
of the above general formulas [I] to [IV], may be formed by a known
process such as vacuum evaporation, molecular-beam evaporation(MBE)
and application of a solution, e.g., dipping, spin coating,
casting, bar coating and roll coating.
There is no limitation for a thickness of each organic layer of an
organic EL device according to this invention. However, in general,
an excessively thin layer tends to cause defects such as a pin
hole, while an excessively thick layer may require higher applied
voltage, resulting in a lower efficiency. The thickness is,
therefore, preferably several nanometers to 1 .mu.m.
This invention will be specifically described with the following
examples, but is not limited to the examples without departing from
its spirit and scope.
EXAMPLES
Preparation Example 1
Preparation of Compound [I]-(3), 9,9'-bianthryl
The title compound, 9,9'-bianthryl, was prepared by treating
9-anthrone with magnesium and iodine as usual.
Preparation Example 2
Preparation of Compound [I]-(4),
10-diphenylamino-9,9'-bianthryl
In a flask were placed 35 g of 9,9'-bianthryl, 18.0 g of
N-bromosuccinimide and 500 mL of carbon tetrachloride, and the
mixture was stirred overnight. The reaction mixture was filtered,
the filtrate was passed through a column filled with alumina.
Carbon tetrachloride was evaporated from the solution under a
reduced pressure, and then the residue was recrystallized from
petroleum ether, to give 35 g(yield: 80%) of
10-bromo-9,9'-bianthryl. Then, in a 100 mL three-necked flask were
placed 18.3 g of 10-bromo-9,9'-bianthryl, 10 g of diphenylamine,
8.5 g of potassium carbonate, 0.2 g of copper powder and 50 mL of
nitrobenzene, and the mixture was stirred at 200.degree. C. for 30
hours. After completion of the reaction, toluene was added to the
mixture. The mixture was filtered to remove inorganics. Toluene and
nitrobenzene were evaporated under a reduced pressure. The residue
was purified by column chromatography on silica gel eluting with a
1:2 mixture of toluene and ligroin, to give 15 g(yield: 60%) of
10-diphenylamino-9,9'-bianthryl.
Preparation Example 3
Preparation of Compound [I]-(5),
10,10'-bis(diphenylamino)-9,9'-bianthryl
In a flask were placed 35 g of 9,9'-bianthryl and 300 mL of carbon
tetrachloride, and to the vigorously stirred mixture was slowly
added 40 g of bromine under cooling. After addition, the mixture
was slowly warmed and then refluxed for 1 hour with stirring.
Carbon tetrachloride was evaporated from the reaction mixture under
a reduced pressure, the residual solid was extracted with carbon
tetrachloride using a Soxhlet extractor. The extract was dried and
concentrated to give 42 g(yield 81%) of
10,10'-dibromo-9,9'-bianthryl. Then, in a 100 mL three-necked flask
were placed 25 g of 10,10'-dibromo-9,9'-bianthryl, 20 g of
diphenylamine, 17 g of potassium carbonate, 0.4 g of copper powder
and 80 mL of nitrobenzene, and the mixture was stirred at
200.degree. C. for 30 hours. After completion of the reaction,
toluene was added to the mixture. The mixture was filtered to
remove inorganics. Toluene and nitrobenzene were evaporated under a
reduced pressure. The residue was purified by column chromatography
on silica gel eluting with a 1:2 mixture of toluene and ligroin, to
give 19 g(yield: 55%) of
10,10'-bis(diphenylamino)-9,9'-bianthryl.
Preparation Example 4
Preparation of Compound [I]-(6),
10-N,N'-di(4-(.alpha.,.alpha.-dimethylbenzyl)phenyl)amino-9,9'-bianthryl
The title compound,
10-N,N'-di(4-(.alpha.,.alpha.-dimethylbenzyl)phenyl)amino-9,9'-bianthryl
(20 g; yield 54%), was prepared as described in Preparation Example
2, except that 10 g of diphenylamine was replaced with 24 g of
N,N-di(4-(.alpha.,.alpha.-dimethylbenzyl)phenyl)amine.
Preparation Example 5
Preparation of Compound [I]-(7),
10,10'-bis(N-phenyl-N-p-styrylphenylamino)-9,9'-bianthryl
10,10'-Bis(p-tolylphenylamino)-9,9'-bianthryl(19 g; yield 54%) was
prepared as described in Preparation Example 3, except that 20 g of
diphenylamine was replaced with 22 g of p-tolylphenylamine. Then, 7
g of 10,10'-bis(p-tolylphenylamino)-9,9'-bianthryl was dissolved in
50 mL of toluene, to which 3.7 g of phosphorus oxychloride was then
added, and the mixture was stirred at room temperature. To the
mixture was added dropwise 2.7 g of N-methylformanilide, and the
mixture was stirred at 50.degree. C. for 5 hours. After completion
of the reaction, the mixture was slowly poured into 100 mL of cold
water. The mixture was transferred into a separatory funnel and the
toluene layer was washed several times until pH of the washing
become neutral. The organic layer was dried over magnesium sulfate
and evaporated to give 4.5 g (yield 60%) of
10,10'-bis(N-p-formylphenyl-N-tolylamino)-9,9'-bianthryl. To 50 mL
of dimethylsulfoxide were added 2.9 g of diethyl benzylphosphonate
and 0.6 g of sodium hydride. To the stirred mixture was added
dropwise 4.5 g of
10,10'-bis(N-p-formylphenyl-N-tolylamino)-9,9'-bianthryl in 50 mL
of dimethylsulfoxide, and the reaction mixture was stirred at
50.degree. C. for 3 hours. After completion of the reaction, the
solution was poured into 50 mL of ice-water. The mixture was
neutralized with an acid and extracted with ethyl acetate. After
evaporating the solvent under a reduced pressure, the residue was
purified by column chromatography on silica gel eluting with
chloroform, and the product was recrystallized from ethanol to give
3.8 g (yield 70%) of
10,10'-bis(N-p-styrylphenyl-N-tolylamino)-9,9'-bianthryl.
Preparation Example 6
Preparation of Compound [II]-(6),
3,3'-dimethyl-4,4'-bis(di-p-tolylamino)-1,1'-binaphthyl
In a 100 mL three-necked flask were placed 2 g of
3,3'-dimethylnaphthydine, 5.6 g of p-iodotoluene, 0.2 g of copper
powder, 2 g of potassium carbonate and 10 mL of nitrobenzene, and
the mixture was stirred at 200.degree. C. for 30 hours. After
completion of the reaction, toluene was added and the mixture was
filtered to remove inorganics. Then, the filtrate was washed with
water, dried over magnesium sulfate and evaporated. The residue was
purified by column chromatography on silica gel eluting with a
mixture of toluene-hexane, to give 2.2 g of
3,3'-dimethyl-4,4'-bis(di-p-tolylamino)-1,1'-binaphthyl.
##STR18##
This compound belongs to the compound represented by the above
general formula [II]-(1).
Preparation Example 7
Preparation of Compound [II]-(7),
3,3'-dimethyl-4,4'-bis(4-styryldiphenylamino)-1,1'-binaphthyl
In a 100 mL three-necked flask were placed 4 g of
3,3'-dimethylnaphthydine, 10.4 g of p-iodobenzene, 0.4 g of copper
powder, 4.0 g of potassium carbonate and 15 mL of nitrobenzene, and
the mixture was stirred at 200.degree. C. for 30 hours. After
completion of the reaction, toluene was added and the mixture was
filtered to remove inorganics. Then, the filtrate was washed with
water, dried over magnesium sulfate and evaporated. The residue was
purified by column chromatography on silica gel eluting with a
mixture of toluene-hexane, to give 4 g of
3,3'-dimethyl-4,4'-bis(diphenylamino)-1,1'-binaphthyl.
In a 50 mL three-necked flask were placed 2 g of
3,3'-dimethyl-4,4'-bis(diphenylamino)-1,1'-binaphthyl, 10 mL of
toluene and 1.1 g of phosphorus oxychloride. To the stirred mixture
was slowly added dropwise 1.0 g of N-methylformanilide, and the
mixture was stirred at room temperature for 1 hour and at
50.degree. C. for 4 hours. After completion of the reaction, the
mixture was poured into cold water and extracted with toluene. The
toluene extract was washed with water, dried over magnesium sulfate
and evaporated. The residue was purified by column chromatography
on silica gel eluting with a mixture of toluene and hexane, to give
1.5 g of
3,3'-dimethyl-4,4'-bis(4-formyldiphenylamino)-1,1'-binaphthyl.
Then, in a 50 mL three-necked flask were placed 1.4 g of diethyl
benzylphosphonate, 0.2 g of sodium hydride and 10 mL of
dimethylsulfoxide. To the stirred mixture was slowly added dropwise
1 g of
3,3'-dimethyl-4,4'-bis(4-formyldiphenylamino)-1,1'-binaphthyl in 5
mL of dimethylsulfoxide, and the mixture was stirred at room
temperature for 1 hour and at 40.degree. C. for 5 hours. After
completion of the reaction, the solution was poured into water and
extracted with toluene. The toluene layer was dried over magnesium
sulfate and evaporated. The residue was purified by column
chromatography on silica gel eluting with a mixture of toluene and
ligroin, to give
3,3'-dimethyl-4,4'-bis(4-styryldiphenylamino)-1,1'-binaphthyl.
##STR19##
This compound belongs to the compound represented by the above
general formula [II]-(2).
Preparation Example 8
Preparation of Compound [III]-(3), tri-9,10-anthrylene
9-Bromoanthracene was reacted with lithium to generate
9-lithioanthracene, which was then reacted with anthraquinone.
Then, the product was reduced with hydrogen iodide and phosphinic
acid to be aromatized, and was purified as usual, to give the
desired tri-9,10-anthrylene.
Preparation Example 9
Preparation of Compound [III]-(4),
10-di-p-tolylaminotri-9,10-anthrylene
In a flask were placed 53 g of tri-9,10-anthrylene obtained as
described in Preparation Example 8 and 18 g of N-bromosuccinimide
in chloroform, and the mixture was stirred overnight.
The reaction mixture was washed with water. The organic layer was
dried and as usual, purified to give
10-bromotri-9,10-anthrylene.
In a three-necked flask were placed 30 g of
10-bromotri-9,10-anthrylene, 9 g of di-p-tolylamine, 3.5 g of
potassium carbonate and 1.5 g of copper powder in nitrobenzene, and
the mixture was stirred at 200.degree. C. for 30 hours.
After completion of the reaction, toluene and chloroform were added
and the mixture was filtered to remove inorganics. Then, toluene,
chloroform and nitrobenzene were evaporated under a reduced
pressure, and the residue was purified as usual, to give the
desired 10-di-p-tolylaminotri-9,10-anthrylene.
Preparation Example 10
Preparation of Compound [III]-(5),
10,10"-bis(di-p-tolylamino)tri-9,10-anthrylene
In a flask were placed 53 g of tri-9,10-anthrylene obtained as
described in Preparation Example 8 and 36 g of N-bromosuccinimide
in chloroform, and the mixture was stirred overnight.
The reaction mixture was washed with water. The organic layer was
dried and as usual, purified to give
10,10"-dibromotri-9,10-anthrylene.
In a three-necked flask were placed 35 g of
10,10"-dibromotri-9,10-anthrylene, 18 g of di-p-tolylamine, 7 g of
potassium carbonate and 3 g of copper powder in nitrobenzene, and
the mixture was stirred at 200.degree. C. for 30 hours.
After completion of the reaction, toluene and chloroform were added
and the mixture was filtered to remove inorganics. Then, toluene,
chloroform and nitrobenzene were evaporated under a reduced
pressure, and the residue was purified as usual, to give the
desired 10,10"-bis(di-p-tolylamino)tri-9,10-anthrylene.
Preparation Example 11
Preparation of Compound [III]-(6),
10-(N-phenyl-N-p-(4-methylphenylvinyl)phenylamino)tri-9,10-anthrylene
10-(N-phenyl-N-p-tolylamino)tri-9,10-anthrylene was prepared as
described in Preparation Example 9, except that 9 g of
di-p-tolylamine was replaced with 8.5 g of
N-phenyl-N-p-tolylamine.
Then, 10-(N-phenyl-N-p-tolylamino)tri-9,10-anthrylene was dissolved
in toluene, to which phosphorus oxychloride was then added, and the
mixture was stirred at room temperature. To the mixture was added
dropwise N-methylformanilide, and the mixture was stirred at
50.degree. C. for 5 hours.
After completion of the reaction, the mixture was slowly poured
into cold water. The mixture was transferred into a separatory
funnel and the toluene layer was washed with water several times
until pH of the washing become neutral. The organic layer was dried
over magnesium sulfate and evaporated to give
10-(N-formylphenyl-N-p-tolylamino)tri-9,10-anthrylene.
To dimethylsulfoxide were added diethyl 4-methylbenzylphosphonate
and sodium hydride. To the stirred mixture was added dropwise
10-(N-formylphenyl-N-p-tolylamino)tri-9,10-anthrylene in
dimethylsulfoxide, and the reaction mixture was stirred at
50.degree. C. for 3 hours.
After completion of the reaction, the solution was poured into
ice-water. The mixture was neutralized with an acid and extracted
with ethyl acetate. After evaporating the solvent under a reduced
pressure, the residue was purified as usual to give the desired
10-(N-phenyl-N-p-(4-methylphenylvinyl)phenylamino)tri-9,10-anthrylene.
Preparation Example 12
Preparation of Compound [III]-(7),
10,10"-bis(N-phenyl-N-p-(4-methylphenylvinyl)phenylamino)tri-9,10-anthryle
ne
10,10"-bis(N-phenyl-N-p-tolylamino)tri-9,10-anthrylene was prepared
as described in Preparation Example 10, except that 18 g of
di-p-tolylamine was replaced with 17 g of
N-phenyl-N-p-tolylamine.
Then, 10,10"-bis(N-phenyl-N-p-tolylamino)tri-9,10-anthrylene was
dissolved in toluene, to which phosphorus oxychloride was then
added, and the mixture was stirred at room temperature. To the
mixture was added dropwise N-methylformanilide, and the mixture was
stirred at 50.degree. C. for 5 hours.
After completion of the reaction, the mixture was slowly poured
into cold water. The mixture was transferred into a separatory
funnel and the toluene layer was washed with water several times
until pH of the washing become neutral. The organic layer was dried
over magnesium sulfate and evaporated to give
10,10"-bis(N-formylphenyl-N-p-tolylamino)tri-9,10-anthrylene.
To dimethylsulfoxide were added diethyl 4-methylbenzylphosphonate
and sodium hydride. To the stirred mixture was added dropwise
10,10"-bis(N-formylphenyl-N-p-tolylamino)tri-9,10-anthrylene in
dimethylsulfoxide, and the reaction mixture was stirred at
50.degree. C. for 3 hours.
After completion of the reaction, the solution was poured into
ice-water. The mixture was neutralized with an acid and extracted
with ethyl acetate. After evaporating the solvent under a reduced
pressure, the residue was purified as usual to give the desired
10,10"-bis(N-phenyl-N-p-(4-methylphenylvinyl)phenylamino)tri-9,10-anthryle
ne.
Preparation Example 13
Preparation of Compound [IV]-(3), 9-.alpha.-naphthylanthracene
A Grignard reagent was prepared from 1-bromonaphthalene and
magnesium in diethyl ether under an inert atmosphere. The reagent
was reacted with 9-anthrone. The reaction was quenched with
hydrochloric acid, and the mixture was purified as usual, to give
the desired 9-.alpha.-naphthylanthracene.
Preparation Example 14
Preparation of Compound [IV]-(4),
10-di-p-tolylamino-9-.alpha.-naphthylanthracene
In a flask were 9-.alpha.-naphthylanthracene and an equivalent
amount of N-bromosuccinimide, and the reaction mixture was stirred
overnight and then filtered. The filtrate was passed through a
column filled with alumina. Chloroform was evaporated from the
solution under a reduced pressure, and then the residue was
recrystallized from petroleum ether, to give
10-chloro-9-.alpha.-naphthylanthracene. Then, in a three-necked
flask were placed 10-chloro-9-.alpha.-naphthylanthracene, an
equivalent amount of di-p-tolylamine, an equivalent amount of
potassium carbonate, copper powder and nitrobenzene, and the
mixture was stirred at 200.degree. C. for 30 hours. After
completion of the reaction, toluene was added to the mixture. The
mixture was filtered to remove inorganics. Toluene and nitrobenzene
were evaporated under a reduced pressure. The residue was purified
by column chromatography on silica gel eluting with a 1:2 mixture
of toluene and ligroin, to give
10-di-p-tolylamino-9-.alpha.-naphthylanthracene.
Preparation Example 15
Preparation of Compound [IV]-(5),
10-di-p-tolylamino-9-(4-di-p-tolylamino-1-naphthyl)anthracene
The title compound,
10-di-p-tolylamino-9-(4-di-p-tolylamino-1-naphthyl)anthracene, was
prepared as described in Preparation Example 14, except that both
N-bromosuccinimide and di-p-tolylamine were used in two equivalent
amount.
Preparation Example 16
Preparation of Compound [IV]-(6),
10-N-(p-tolylvinylphenyl)-N-p-tolylamino-9-(4-N-(p-tolylvinylphenyl)-N-p-t
olylamino-1-naphthyl)anthracene
10-N-Phenyl-N-p-tolylamino-9-(4-N-phenyl-N-p-tolylamino-1-naphthyl)anthrace
ne was prepared as described in Preparation Example 16, except that
di-p-tolylamine was replaced with p-tolylphenylamine. In toluene
was dissolved
10-N-Phenyl-N-p-tolylamino-9-(4-N-phenyl-N-p-tolylamino-1-naphthyl)anthrac
ene. Phosphorus oxychloride was added to the solution and the
mixture was then stirred at room temperature. To the stirred
mixture was added dropwise N-methylformanilide, and the mixture was
stirred at 50.degree. C. for 5 hours. After completion of the
reaction, the mixture was slowly poured into cold water. The
mixture was transferred into a separatory funnel. The toluene layer
was washed several times with water until pH of the washing became
neutral, dried over magnesium sulfate and evaporated, to give
10-N-(p-formylphenyl)-N-p-tolylamino-9-(4-N-(p-formylphenyl)-N-p-tolylamin
o-1-naphthyl)anthracene. Then, to dimethylsulfoxide was added
diethyl 4-methylbenzylphosphonate and sodium hydride. To the
stirred mixture was added dropwise
10-N-(p-formylphenyl)-N-p-tolylamino-9-(4-N-(p-formylphenyl)-N-p-tolylamin
o-1-naphthyl)anthracene in dimethylsulfoxide, and then the mixture
was stirred at 50.degree. C. for 3 hours. After completion of the
reaction, the reaction solution was poured into ice-water and
extracted with ethyl acetate. After evaporating the solvent under a
reduced pressure, the residue was purified by column chromatography
on silica gel eluting with chloroform, and the product was
recrystallized from ethanol, to give
10-N-(p-tolylvinylphenyl)-N-p-tolylamino-9-(4-N-(p-tolylvinylphenyl)-N-p-t
olylamino-1-naphthyl)anthracene.
The followings are examples where a compound in [I] is used as a
luminescent layer (Examples 1 to 11); a mixture layer of the
compound and a hole-transporting material as a luminescent layer
(Examples 12 to 14); a mixture layer of the compound and an
electron-transporting material as a luminescent layer (Examples 15
and 16), the compound as a hole-transporting layer (Examples 17 to
21) or the compound as an electron-transporting layer (Examples 22
to 26).
Example 1
FIG. 1 shows the cross section of the device in this example. A
procedure for preparing an organic EL device of this invention will
be described. The device consists of an anode 2/a luminescent layer
4/a cathode 6. On a glass substrate 1, ITO was deposited as an
anode 2 by spattering, with a sheet resistance of 20
.OMEGA./.quadrature.. On the anode 2, Compound [I]-(3) was
deposited to 40 nm thick as a luminescent layer 4, by vacuum
evaporation. Then, magnesium-silver alloy as a cathode 6 was
deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device. Applying 5 V DC to the device generated a
luminescence of 100 cd/m.sup.2.
Example 2
An organic EL device was prepared as described in Example 1, except
using Compound [I]-(4) as a luminescent material. Applying 5 V DC
to the device generated a luminescence of 200 cd/m.sup.2.
Example 3
An organic EL device was prepared as described in Example 1, except
using Compound [I]-(5) as a luminescent material. Applying 5 V DC
to the device generated a luminescence of 250 cd/m.sup.2.
Example 4
An organic EL device was prepared as described in Example 1, except
using Compound [I]-(6) as a luminescent material. Applying 5 V DC
to the device generated a luminescence of 400 cd/m.sup.2.
Example 5
An organic EL device was prepared as described in Example 1, except
using Compound [I]-(7) as a luminescent material. Applying 5 V DC
to the device generated a luminescence of 500 cd/m.sup.2.
Example 6
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was formed a luminescent layer 40 nm thick, by spin coating with a
solution of Compound [I]-(5) in chloroform. Then, magnesium-silver
alloy as a cathode was deposited to 200 nm thick, by vacuum
evaporation, to give an organic EL device. Applying 5 V DC to the
device generated a luminescence of 120 cd/m.sup.2.
Example 7
FIG. 2 shows the cross section of the device in this example. The
device consists of an anode 2/a hole-transporting layer 3/a
luminescent layer 4/an electron-transporting layer 5/a cathode 6.
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was deposited
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine[02]
50 nm thick as a hole-transporting layer by vacuum evaporation.
Then, Compound [I]-(3) was deposited to 40 nm thick as a
luminescent layer , by vacuum evaporation. Then,
2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole[07] was
deposited to 20 nm thick as an electron-transporting layer, by
vacuum evaporation. Then, magnesium-silver alloy as a cathode was
deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device. Applying 10 V DC to the device generated a
luminescence of 1000 cd/m.sup.2.
Example 8
An organic EL device was prepared as described in Example 7, except
using Compound [I]-(5) as a luminescent material. Applying 10 V DC
to the device generated a luminescence of 2000 cd/m.sup.2.
Example 9
An organic EL device was prepared as described in Example 7, except
using
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
as a hole-transporting layer and
bis{2-(4-t-butylphenyl)-1,3,4-oxadiazole}-m-phenylene[08] as an
electron-transporting layer. Applying 10 V DC to the device
generated a luminescence of 1500 cd/m.sup.2.
Example 10
An organic EL device was prepared as described in Example 7, except
using Compound [04] as a hole-transporting layer, Compound [I]-(5)
as a luminescent layer and Compound [9] as an electron-transporting
layer. Applying 14 V DC to the device generated a luminescence of
2000 cd/m.sup.2.
Example 11
An organic EL device was prepared as described in Example 7, except
using Compound [05] as a hole-transporting layer, Compound [I]-(7)
as a luminescent layer and Compound [12] as an
electron-transporting layer. Applying 10 V DC to the device
generated a luminescence of 2600 cd/m.sup.2.
Example 12
FIG. 4 shows the cross section of the device in this example. The
device consists of an anode/a luminescent layer/an
electron-transporting layer/a cathode. On a glass substrate, ITO
was deposited as an anode by spattering, with a sheet resistance of
20 .OMEGA./.quadrature.. On the anode was co-deposited in vacuo
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
and Compound [I]-(3) (1:10 by weight) 50 nm thick as a luminescent
layer. Then, Compound [9] was deposited to 50 nm thick as an
electron-transporting layer, by vacuum evaporation. Then,
magnesium-silver alloy as a cathode was deposited to 200 nm thick,
to give an organic EL device. Applying 10 V DC to the device
generated a luminescence of 1200 cd/m.sup.2.
Example 13
An organic EL device was prepared as described in Example 12,
except using Compound [I]-(5) in place of Compound [I]-(3).
Applying 10 V DC to the device generated a luminescence of 2100
cd/m.sup.2.
Example 14
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was formed a luminescent layer 40 nm thick, by spin coating with a
solution of Compound [I]-(5) and
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
(1:10 molar ratio) in chloroform. Then, Compound [10] was deposited
to 50 nm thick as an electron-transporting layer, by vacuum
evaporation. Then, magnesium-silver alloy as a cathode was
deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device. Applying 10 V DC to the device generated a
luminescence of 1000 cd/m.sup.2.
Example 15
FIG. 3 shows the cross section of the device in this example. The
device consists of an anode/a hole-transporting layer/a luminescent
layer/a cathode. On a glass substrate, ITO was deposited as an
anode by spattering, with a sheet resistance of 20
.OMEGA./.quadrature.. On the anode was deposited
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
50 nm thick as a hole-transporting layer, by vacuum evaporation.
Then, Compounds [11] and [I]-(3) (20:1 by weight) were deposited to
50 nm thick as a luminescent layer, by vacuum evaporation. Then,
magnesium-silver alloy as a cathode was deposited to 200 nm thick,
to give an organic EL device. Applying 10 V DC to the device
generated a luminescence of 1300 cd/m.sup.2.
Example 16
An organic EL device was prepared as described in Example 15,
except co-depositing in vacuo Compounds [11] and [I]-(5) (20:1 by
weight) as a luminescent layer. Applying 10 V DC to the device
generated a luminescence of 2200 cd/m.sup.2.
Example 17
An organic EL device was prepared as described in Example 15,
except using
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine[02]
as a hole-transporting layer and co-depositing in vacuo Compounds
[13] and [I]-(7) (20:1 by weight) as a luminescent layer. Applying
10 V DC to the device generated a luminescence of 2500
cd/m.sup.2.
Example 18
An organic EL device was prepared as described in Example 7, except
using Compound [I]-(4) as a hole-transporting layer and Compound
[13] as a luminescent layer. Applying 10 V DC to the device
generated a luminescence of 800 cd/m.sup.2.
Example 19
An organic EL device was prepared as described in Example 18,
except using Compound [I]-(5) as a hole-transporting layer.
Applying 10 V DC to the device generated a luminescence of 1200
cd/m.sup.2.
Example 20
An organic EL device was prepared as described in Example 18,
except using Compound [I]-(6) as a hole-transporting layer.
Applying 10 V DC to the device generated a luminescence of 1300
cd/m.sup.2.
Example 21
An organic EL device was prepared as described in Example 18,
except using Compound [I]-(7) as a hole-transporting layer.
Applying 10 V DC to the device generated a luminescence of 1500
cd/m.sup.2.
Example 22
An organic EL device was prepared as described in Example 7, except
using
N,N'-diphenyl-bis(1-naphthyl)-(1,1'-biphenyl)-4,4'-diamine[03] as a
hole-transporting layer, Compound [13] as a luminescent layer and
Compound [I]-(3) as an electron-transporting layer. Applying 10 V
DC to the device generated a luminescence of 1000 cd/m.sup.2.
Example 23
An organic EL device was prepared as described in Example 22,
except using Compound [I]-(4) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 800
cd/m.sup.2.
Example 24
An organic EL device was prepared as described in Example 22,
except using Compound [I]-(5) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 500
cd/m.sup.2.
Example 25
An organic EL device was prepared as described in Example 22,
except using Compound [I]-(6) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 700
cd/m.sup.2.
Example 26
An organic EL device was prepared as described in Example 22,
except using Compound [I]-(7) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 400
cd/m.sup.2.
The followings are examples where a compound in [II] is used as a
luminescent layer (Examples 27 to 37); a mixture layer of the
compound and a hole-transporting material as a luminescent layer
(Examples 38 to 40); a mixture layer of the compound and an
electron-transporting material as a luminescent layer (Examples 41
and 43), the compound as a hole-transporting layer (Examples 44 to
46) or the compound as an electron-transporting layer (Examples 47
to 51).
Example 27
The cross section of the organic thin-layer EL device in this
example is shown in FIG. 1, whose preparation procedure is as
described in Example 1. The EL device consists of an anode 2/a
luminescent layer 4/a cathode 6. On a glass substrate 1, ITO was
deposited as an anode 2 by spattering, with a sheet resistance of
20 .OMEGA./.quadrature.. On the anode 2, a thin layer of
4-(di-p-tolylamino)-1,1'-binaphthyl([II]-(8)) was deposited to 40
nm thick as a luminescent layer 4, by vacuum evaporation.
##STR20##
Then, magnesium-silver alloy as a cathode 6 was deposited to 200 nm
thick, by vacuum evaporation, to give an organic EL device.
Applying 5 V DC to the device generated a luminescence of 150
cd/m.sup.2.
Example 28
A similar organic EL device was prepared as described in Example
27, except using
3,3'-dimethyl-4,4'-bis(4-methyldiphenylamino)-1,1'-binaphthyl([II]-(9))
as a luminescent material. ##STR21##
Applying 5 V DC to the device generated a luminescence of 250
cd/m.sup.2.
Example 29
A similar organic EL device was prepared as described in Example
27, except using
3,3'-dimethyl-4,4'-bis(di-p-tolylamino)-1,1'-binaphthyl([II]-(6))
as a luminescent material. Applying 5 V DC to the device generated
a luminescence of 250 cd/m.sup.2.
Example 30
A similar organic EL device was prepared as described in Example
27, except using
3,3'-dimethyl-4,4'-bis(phenyl-p-.beta.-styrylphenylamino)-1,1'-binaphthyl(
[II]-(7)) as a luminescent material. Applying 5 V DC to the device
generated a luminescence of 480 cd/m.sup.2.
Example 31
A similar organic EL device was prepared as described in Example
27, except using Compound [II]-(5) as a luminescent material.
Applying 5 V DC to the device generated a luminescence of 650
cd/m.sup.2.
Example 32
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was formed a luminescent layer 40 nm thick, by spin coating with a
solution of 4,4'-bis(diphenylamino)-1,1'-binaphthyl([II]-(3)) in
chloroform. ##STR22##
Then, magnesium-silver alloy as a cathode was deposited to 200 nm
thick, by vacuum evaporation, to give an organic EL device as shown
in FIG. 1. Applying 5 V DC to the device generated a luminescence
of 120 cd/m.sup.2.
Example 33
The device of this example has the cross section shown in FIG. 2
and described in Example 7. The EL device consists of an anode 2/a
hole-transporting layer 3/a luminescent layer 4/an
electron-transporting layer 5/a cathode 6. On a glass substrate 1,
ITO was deposited as an anode 2 by spattering, with a sheet
resistance of 20 .OMEGA./.quadrature.. On the anode was deposited a
thin layer of
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine[02]
50 nm thick as a hole-transporting layer 3. Then, a thin layer of
3,3'-dimethyl-4,4'-bis(4-methyldiphenylamino)-1,1'-binaphthyl([II]-(9))
was deposited to 40 nm thick as a luminescent layer 4, by vacuum
evaporation. Then, a thin layer of
2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole[07] was
deposited to 20 nm thick as an electron-transporting layer 5, by
vacuum evaporation. Finally, magnesium-silver alloy as a cathode 6
was deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device. Applying 10 V DC to the device generated a
luminescence of 1200 cd/m.sup.2.
Example 34
An organic EL device as shown in FIG. 2 was prepared as described
in Example 7, except using Compound [II]-(7) as a luminescent
material. Applying 10 V DC to the device generated a luminescence
of 2500 cd/m.sup.2.
Example 35
An organic EL device as shown in FIG. 2 was prepared as described
in Example 33, except using
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
as a hole-transporting material and
bis{2-(4-t-butylphenyl)-1,3,4-oxadiazole}-m-phenylene[08] as an
electron-transporting material. Applying 10 V DC to the device
generated a luminescence of 1600 cd/m.sup.2.
Example 36
An organic EL device as shown in FIG. 2 was prepared as described
in Example 33, except using Compound [04] as a hole-transporting
material, Compound [II]-(7) as a luminescent material and Compound
[11] as an electron-transporting material. Applying 10 V DC to the
device generated a luminescence of 2700 cd/m.sup.2.
Example 37
An organic EL device as shown in FIG. 2 was prepared as described
in Example 33, except using Compound [05] as a hole-transporting
material, Compound [II]-(5) as a luminescent material and Compound
[12] as an electron-transporting material. Applying 10 V DC to the
device generated a luminescence of 3200 cd/m.sup.2.
Example 38
The EL device of this example has a cross section as shown in FIG.
4. The device consists of an anode 2/a luminescent layer 4/an
electron-transporting layer 5/a cathode 6. On a glass substrate 1,
ITO was deposited as an anode 2 by spattering, with a sheet
resistance of 20 .OMEGA./cm/cm. On the anode was co-deposited in
vacuo a thin layer of
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine[03]
and
3,3'-dimethyl-4,4'-bis(4-methyldiphenylamino)-1,1'-binaphthyl([II]-(9))
(1:10 ratio by weight) 50 nm thick as a luminescent layer 4. Then,
a thin layer of Compound [09] was deposited to 50 nm thick as an
electron-transporting layer 5, by vacuum evaporation. Then, a thin
layer of magnesium-silver alloy as a cathode 6 was deposited to 200
nm thick, to give an EL device. Applying 10 V DC to the device
generated a luminescence of 1200 cd/m.sup.2.
Example 39
An organic EL device as shown in FIG. 4 was prepared as described
in Example 38, except using
3,3'-dimethyl-4,4'-bis(4-.beta.-styryldiphenylamino)-1,1'-binaphthyl([II]-
(6)) in place of
3,3'-dimethyl-4,4'-bis(4-methyldiphenylamino)-1,1'-binaphthyl([II]-(9)).
Applying 10 V DC to the device generated a luminescence of 2100
cd/m.sup.2.
Example 40
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was formed a luminescent layer 40 nm thick, by spin coating with a
solution of
3,3'-dimethyl-4,4'-bis(4-.beta.-styryldiphenylamino)-1,1'-binaphthyl([II]-
(7)) and
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
(1:10 molar ratio) in chloroform. Then, Compound [10] was deposited
to 50 nm thick as an electron-transporting layer, by vacuum
evaporation. Then, magnesium-silver alloy as a cathode was
deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device as shown in FIG. 4. Applying 10 V DC to the
device generated a luminescence of 1100 cd/m.sup.2.
Example 41
This example will describe a device as shown in FIG. 3. On a glass
substrate 1, ITO was deposited as an anode 2 by spattering, with a
sheet resistance of 20 .OMEGA./cm/cm. On the anode was deposited a
thin layer of
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
50 nm thick as a hole-transporting layer 3, by vacuum evaporation.
Then, a thin layer of Compound [11] and
3,3'-dimethyl-4,4'-bis(4-methyldiphenylamino)-1,1'-binaphthyl([II]-(9))
(20:1 by weight) were deposited to 50 nm thick as a luminescent
layer 4, by vacuum evaporation. Then, magnesium-silver alloy as a
cathode 6 was deposited to 200 nm thick, to give an EL device.
Applying 10 V DC to the device generated a luminescence of 1500
cd/m.sup.2.
Example 42
An organic EL device as shown in FIG. 3 was prepared as described
in Example 41, except co-depositing in vacuo Compound [11] and
3,3'-dimethyl-4,4'-bis(4-.beta.-styryldiphenylamino)-1,1'-binaphthyl([II]-
(7)) (20:1 by weight) as a luminescent layer. Applying 10 V DC to
the device generated a luminescence of 2000 cd/m.sup.2.
Example 43
An organic EL device as shown FIG. 3 was prepared as described in
Example 41, except using
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine[02]
as a hole-transporting material and co-depositing in vacuo
Compounds [13] and [II]-(5) (20:1 by weight) as a luminescent
layer. Applying 10 V DC to the device generated a luminescence of
2500 cd/m.sup.2.
Example 44
An organic EL device as shown in FIG. 3 was prepared as described
in Example 33, except using
3,3'-dimethyl-4,4'-bis(4-.beta.-styryldiphenylamino)-1,1'-binaphthyl([II]-
(7)) as a hole-transporting material and Compound [13] as a
luminescent layer. Applying 10 V DC to the device generated a
luminescence of 1200 cd/m.sup.2.
Example 45
An organic EL device as shown in FIG. 3 was prepared as described
in Example 44, except using Compound [II]-(4) as a
hole-transporting material. Applying 10 V DC to the device
generated a luminescence of 1300 cd/m.sup.2.
Example 46
An organic EL device as shown in FIG. 3 was prepared as described
in Example 44, except using Compound [II]-(5) as a
hole-transporting material. Applying 10 V DC to the device
generated a luminescence of 1500 cd/m.sup.2.
Example 47
An organic EL device as shown in FIG. 3 was prepared as described
in Example 33, except using
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine[03]
as a hole-transporting material, Compound [13] as a luminescent
material and
3,3'-dimethyl-4,4'-bis(4-methyldiphenylamino)-1,1'-binaphthyl([II]-(9))
as an electron-transporting material. Applying 10 V DC to the
device generated a luminescence of 1000 cd/m.sup.2.
Example 48
An organic EL device as shown in FIG. 3 was prepared as described
in Example 47, except using
3,3'-dimethyl-4,4'-bis(di-p-tolylamino)-1,1'-binaphthyl([II]-(6))
as an electron-transporting material. Applying 10 V DC to the
device generated a luminescence of 800 cd/m.sup.2.
Example 49
An organic EL device as shown in FIG. 3 was prepared as described
in Example 47, except using
3,3'-dimethyl-4,4'-bis(4-.beta.-styryldiphenylamino)-1,1'-binaphthyl([II]-
(7)) as an electron-transporting material. Applying 10 V DC to the
device generated a luminescence of 500 cd/m.sup.2.
Example 50
An organic EL device as shown in FIG. 3 was prepared as described
in Example 47, except using Compound [II]-(4) as an
electron-transporting material. Applying 10 V DC to the device
generated a luminescence of 700 cd/m.sup.2.
Example 51
An organic EL device as shown in FIG. 3 was prepared as described
in Example 47, except using Compound [II]-(5) as an
electron-transporting material. Applying 10 V DC to the device
generated a luminescence of 400 cd/m.sup.2.
Different embodiments of this invention will be specifically
described with examples of an organic EL device in which a compound
in [III] is used.
In Examples 52 to 62, only a compound in [III] is used for a
luminescent layer of an organic EL device. In Examples 63 to 68, a
mixture comprising a compound in [III] is used in a luminescent
layer. In Examples 69 to 72, a compound in [III] is used in a
hole-transporting layer. In Example 73, a compound in [III] is used
in an electron-transporting layer.
Example 52
The organic EL device of this example consists of a substrate 1 on
which a laminated film consisting of an anode 2, a luminescent
layer 4 and a cathode 6 is formed, as shown in FIG. 1.
On a glass substrate 1, ITO was deposited as an anode 2 by
spattering, with a sheet resistance of 20 .OMEGA./.quadrature.. On
the anode 2, a layer of Compound [III]-(3) was deposited to 40 nm
thick as a luminescent layer 4, by vacuum evaporation. Then,
magnesium-silver alloy as a cathode 6 was deposited to 200 nm
thick, by vacuum evaporation, to give an organic EL device.
Applying 5 V DC to the organic EL device generated a luminescence
with a luminance of 90 cd/m.sup.2.
Example 53
An analogous organic EL device was prepared as described in Example
52, except forming a luminescent layer 4 from Compound
[III]-(4).
Applying 5 V DC to the organic EL device generated a luminescence
with a luminance of 250 cd/m.sup.2.
Example 54
An analogous organic EL device was prepared as described in Example
52, except forming a luminescent layer 4 from Compound
[III]-(5).
Applying 5 V DC to the organic EL device generated a luminescence
with a luminance of 300 cd/m.sup.2.
Example 55
An analogous organic EL device was prepared as described in Example
52, except forming a luminescent layer 4 from Compound
[III]-(6).
Applying 5 V DC to the organic EL device generated a luminescence
with a luminance of 480 cd/m.sup.2.
Example 56
An analogous organic EL device was prepared as described in Example
52, except forming a luminescent layer 4 from Compound
[III]-(7).
Applying 5 V DC to the organic EL device generated a luminescence
with a luminance of 600 cd/m.sup.2.
Example 57
An analogous organic EL device was prepared as described in Example
52, except forming a luminescent layer 4(40 nm thick) on an anode
2, by spin coating with a solution of Compound [III]-(7) in
chloroform.
Applying 5 V DC to the organic EL device generated a luminescence
with a luminance of 210 cd/m.sup.2.
Example 58
The organic EL device of this example has a cross section as shown
in FIG. 2.
The device consists of a substrate 1 on which a laminated film
consisting of an anode 2, a hole-transporting layer 3, a
luminescent layer 4, an electron-transporting layer 5 and a cathode
6, as shown in FIG. 2.
On a glass substrate 1, ITO was deposited as an anode 2 by
spattering, with a sheet resistance of 20 .OMEGA./.quadrature.. On
the anode 2 was deposited
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine(Compou
nd [02]) 50 nm thick as a hole-transporting layer 3, by vacuum
evaporation.
Then, Compound [III]-(3) was deposited to 40 nm thick as a
luminescent layer 4, by vacuum evaporation. Then,
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole(Compound
[07]) was deposited to 20 nm thick as an electron-transporting
layer 5, by vacuum evaporation. Then, magnesium-silver alloy as a
cathode was deposited to 200 nm thick, by vacuum evaporation, to
give an organic EL device.
Applying 10 V DC to the device generated a luminescence with a
luminance of 920 cd/m.sup.2.
Example 59
An analogous organic EL device was prepared as described in Example
58, except forming a luminescent layer 4 from Compound
[III]-(4).
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 3000 cd/m.sup.2.
Example 60
An analogous organic EL device was prepared as described in Example
58, except forming a hole-transporting layer 3 from
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine(Compound
[03]) and an electron-transporting layer 5 from
bis{2-(4-t-butylphenyl)-1,3,4-oxadiazole}-m-phenylene(Compound
[08]).
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 1200 cd/m.sup.2.
Example 61
An analogous organic EL device was prepared as described in Example
58, except forming a hole-transporting layer 3 from Compound [04],
a luminescent layer 4 from Compound [III]-(5) and an
electron-transporting layer 5 from Compound [11].
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 3400 cd/m.sup.2.
Example 62
An analogous organic EL device was prepared as described in Example
58, except forming a hole-transporting layer 3 from Compound [05],
a luminescent layer 4 from Compound [III]-(7) and an
electron-transporting layer 5 from Compound [12].
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 4500 cd/m.sup.2.
Example 63
The organic EL device as shown FIG. 3 will be described.
The device of this example consists of a substrate 1 on which a
laminated film consisting of an anode 2, a luminescent layer 4, an
electron-transporting layer 5 and a cathode 6, as shown in FIG.
3.
On a glass substrate 1, ITO was deposited as an anode 2 by
spattering, with a sheet resistance of 20 .OMEGA./.quadrature.. On
the anode 2 was co-deposited in vacuo
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine(Compound
[03]) and Compound [III]-(3) (1:10 by weight) 50 nm thick as a
luminescent layer 4.
Then, on the luminescent layer 4 was deposited Compound [09] 50 nm
thick as an electron-transporting layer 5, by vacuum evaporation.
Then, on the electron-transporting layer 5, magnesium-silver alloy
as a cathode 6 was deposited to 200 nm thick, by vacuum
evaporation, to give an organic EL device.
Applying 10 V DC to the device generated a luminescence with a
luminance of 900 cd/m.sup.2.
Example 64
An analogous organic EL device was prepared as described in Example
63, except using Compound [III]-(5) in place of Compound [III]-(3)
as a material for a luminescent layer 4.
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 2300 cd/m.sup.2.
Example 65
An analogous organic EL device was prepared as described in Example
63, except forming a luminescent layer 4 (40 nm thick) by spin
coating with a solution of Compound [III]-(7) and
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine(Compound
[03]) (1:10 molar ratio) in chloroform, and using Compound [10] as
a material for an electron-transporting layer 5.
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 900 cd/m.sup.2.
Example 66
The organic EL device as shown FIG. 4 will be described.
The device of this example consists of a substrate 1 on which a
laminated film consisting of an anode 2, a hole-transporting layer
3, a luminescent layer 4 and a cathode 6, as shown in FIG. 4.
On a glass substrate 1, ITO was deposited as an anode 2 by
spattering, with a sheet resistance of 20 .OMEGA./.quadrature.. On
the anode 2 was deposited
N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine(Compound
[03]) 50 nm thick as a hole-transporting layer 3, by vacuum
evaporation.
Then, a luminescent layer 4 was formed by co-depositing in vacuo
Compounds [11] and [III]-(3) (20:1 by weight) 50 nm thick. Then,
magnesium-silver alloy as a cathode 6 was deposited to 200 nm
thick, to give an organic EL device.
Applying 10 V DC to the device generated a luminescence with a
luminance of 1100 cd/m.sup.2.
Example 67
An analogous organic EL device was prepared as described in Example
66, except co-depositing in vacuo Compounds [11] and [III]-(5)
(20:1 by weight) 50 nm thick as a luminescent layer 4.
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 1800 cd/m.sup.2.
Example 68
An analogous organic EL device was prepared as described in Example
66, except forming a hole-transporting layer 3 using
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine(Compou
nd [02]), and co-depositing in vacuo Compounds [13] and [III]-(7)
(20:1 by weight) as a luminescent layer 4.
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 2300 cd/m.sup.2.
Example 69
An analogous organic EL device was prepared as described in Example
58, except forming a hole-transporting layer 3 and a luminescent
layer 4 using Compounds [III]-(4) and [13], respectively.
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 850 cd/m.sup.2.
Example 70
An analogous organic EL device was prepared as described in Example
69, except forming a hole-transporting layer 3 using Compound
[III]-(5).
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 1300 cd/m.sup.2.
Example 71
An analogous organic EL device was prepared as described in Example
69, except forming a hole-transporting layer 3 using Compound
[III]-(6).
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 1500 cd/m.sup.2.
Example 72
An analogous organic EL device was prepared as described in Example
69, except forming a hole-transporting layer 3 using Compound
[III]-(7).
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 1800 cd/m.sup.2.
Example 73
An analogous organic EL device was prepared as described in Example
58, except forming a hole-transporting layer 3, a luminescent layer
4 and an electron-transporting layer 5 using
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine(Compound
[03]), Compound [13] and Compound [III]-(3), respectively.
Applying 10 V DC to the organic EL device generated a luminescence
with a luminance of 980 cd/m.sup.2.
Among the organic EL devices of Examples 52 to 57 whose
luminescence properties were tested by applying 5 V DC, the device
of Example 56 using Compound [III]-(7) showed the highest
luminance. Among the organic EL devices of Examples 58 to 73 whose
luminescence properties were tested by applying 10 V DC, the device
of Example 62, in which a luminescent layer comprising Compound
[III]-(7) is inserted between a hole-transporting layer and an
electron-transporting layer, showed the highest luminance.
This demonstrates that Compound [III]-(7) is remarkably effective
for improving luminescence properties of an EL device.
The followings are examples where a compound in [IV] is used as a
luminescent layer (Examples 74 to 82); a mixture layer of the
compound and a hole-transporting material as a luminescent layer
(Examples 83 to 85); a mixture layer of the compound and an
electron-transporting material as a luminescent layer (Examples 86
and 87), the compound as a hole-transporting layer (Examples 88 to
91) or the compound as an electron-transporting layer (Examples 92
to 95).
Example 74
FIG. 1 shows the cross section of the device in this example, whose
preparation procedure is similar to that in Example 1. The device
consists of an anode 2/a luminescent layer 4/a cathode 6. On a
glass substrate 1, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode,
Compound [IV]-(3) was deposited to 40 nm thick as a luminescent
layer, by vacuum evaporation. Then, magnesium-silver alloy as a
cathode was deposited to 200 nm thick, by vacuum evaporation, to
give an organic EL device. Applying 5 V DC to the device generated
a luminescence of 20 cd/m.sup.2.
Example 75
An organic EL device was prepared as described in Example 74,
except using Compound [IV]-(4) as a luminescent material. Applying
5 V DC to the device generated a luminescence of 100
cd/m.sup.2.
Example 76
An organic EL device was prepared as described in Example 74,
except using Compound [IV]-(5) as a luminescent material. Applying
5 V DC to the device generated a luminescence of 400
cd/m.sup.2.
Example 77
An organic EL device was prepared as described in Example 74,
except using Compound [IV]-(6) as a luminescent material. Applying
5 V DC to the device generated a luminescence of 600
cd/m.sup.2.
Example 78
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was formed a luminescent layer 40 nm thick, by spin coating with a
solution of Compound [IV]-(6) in chloroform. Then, magnesium-silver
alloy as a cathode was deposited to 200 nm thick, by vacuum
evaporation, to give an organic EL device. Applying 5 V DC to the
device generated a luminescence of 120 cd/m.sup.2.
Example 79
FIG. 2 shows the cross section of the device in this example. The
device consists of an anode 2/a hole-transporting layer 3/a
luminescent layer 4/an electron-transporting layer 5/a cathode 6.
On a glass substrate 1, ITO was deposited as an anode by
spattering, with a sheet resistance of 20 .OMEGA./.quadrature.. On
the anode was deposited
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine[02]
50 nm thick as a hole-transporting layer by vacuum evaporation.
Then, Compound [IV]-(3) was deposited to 40 nm thick as a
luminescent layer , by vacuum evaporation. Then,
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole[07] was
deposited to 20 nm thick as an electron-transporting layer, by
vacuum evaporation. Then, magnesium-silver alloy as a cathode was
deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device. Applying 10 V DC to the device generated a
luminescence of 800 cd/m.sup.2.
Example 80
An organic EL device was prepared as described in Example 79,
except using Compound [IV]-(4) as a luminescent material. Applying
10 V DC to the device generated a luminescence of 1800
cd/m.sup.2.
Example 81
An organic EL device was prepared as described in Example 79,
except using
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine[03] as
a hole-transporting layer and
bis{2-(4-t-butylphenyl)-1,3,4-oxadiazole}-m-phenylene[08] as an
electron-transporting layer. Applying 10 V DC to the device
generated a luminescence of 1300 cd/m.sup.2.
Example 82
An organic EL device was prepared as described in Example 79,
except using Compound [05] as a hole-transporting layer, Compound
[IV]-(6) as a luminescent layer and Compound [12] as an
electron-transporting layer. Applying 10 V DC to the device
generated a luminescence of 6000 cd/m.sup.2.
Example 83
FIG. 4 shows the cross section of the device in this example. The
device consists of an anode 2/a luminescent layer 4/an
electron-transporting layer 5/a cathode 6. On a glass substrate 1,
ITO was deposited as an anode by spattering, with a sheet
resistance of 20 .OMEGA./.quadrature.. On the anode was
co-deposited in vacuo
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine[03]
and Compound [IV]-(3) (1:10 by weight) 50 nm thick as a luminescent
layer. Then, Compound [9] was deposited to 50 nm thick as an
electron-transporting layer, by vacuum evaporation. Then,
magnesium-silver alloy as a cathode was deposited to 200 nm thick,
to give an organic EL device. Applying 10 V DC to the device
generated a luminescence of 970 cd/m.sup.2.
Example 84
An organic EL device was prepared as described in Example 83,
except using Compound [IV]-(4) in place of Compound [IV]-(3).
Applying 10 V DC to the device generated a luminescence of 2200
cd/m.sup.2.
Example 85
On a glass substrate, ITO was deposited as an anode by spattering,
with a sheet resistance of 20 .OMEGA./.quadrature.. On the anode
was formed a luminescent layer 40 nm thick, by spin coating with a
solution of Compound [IV]-(6) and
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
(1:10 molar ratio) in chloroform. Then, Compound [10] was deposited
to 50 nm thick as an electron-transporting layer, by vacuum
evaporation. Then, magnesium-silver alloy as a cathode was
deposited to 200 nm thick, by vacuum evaporation, to give an
organic EL device. Applying 10 V DC to the device generated a
luminescence of 1300 cd/m.sup.2.
Example 86
FIG. 3 shows the cross section of the device in this example. The
device consists of an anode 2/a hole-transporting layer 3/a
luminescent layer 4/a cathode 6. On a glass substrate 1, ITO was
deposited as an anode by spattering, with a sheet resistance of 20
.OMEGA./.quadrature.. On the anode was deposited
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl)-4,4'-diamine[03]
50 nm thick as a hole-transporting layer, by vacuum evaporation.
Then, Compounds [11] and [IV]-(3) (20:1 by weight) were deposited
to 50 nm thick as a luminescent layer, by vacuum evaporation. Then,
magnesium-silver alloy as a cathode was deposited to 200 nm thick,
to give an organic EL device. Applying 10 V DC to the device
generated a luminescence of 1150 cd/m.sup.2.
Example 87
An organic EL device was prepared as described in Example 86,
except co-depositing in vacuo Compounds [11] and [IV]-(4) (20:1 by
weight) as a luminescent layer. Applying 10 V DC to the device
generated a luminescence of 2100 cd/m.sup.2.
Example 88
An organic EL device was prepared as described in Example 86,
except using
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine[02]
as a hole-transporting layer and co-depositing in vacuo Compounds
[13] and [IV]-(6) (20:1 by weight) as a luminescent layer. Applying
10 V DC to the device generated a luminescence of 3000
cd/m.sup.2.
Example 89
An organic EL device was prepared as described in Example 79,
except using Compound [IV]-(4) as a hole-transporting layer and
Compound [13] as a luminescent layer. Applying 10 V DC to the
device generated a luminescence of 800 cd/m.sup.2.
Example 90
An organic EL device was prepared as described in Example 89,
except using Compound [IV]-(5) as a hole-transporting layer.
Applying 10 V DC to the device generated a luminescence of 1300
cd/m.sup.2.
Example 91
An organic EL device was prepared as described in Example 89,
except using Compound [IV]-(6) as a hole-transporting layer.
Applying 10 V DC to the device generated a luminescence of 1800
cd/m.sup.2.
Example 92
An organic EL device was prepared as described in Example 79,
except using
N,N'-diphenyl-N,N-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine[03] as
a hole-transporting layer, Compound [13] as a luminescent layer and
Compound [IV]-(3) as an electron-transporting layer. Applying 10 V
DC to the device generated a luminescence of 890 cd/m.sup.2.
Example 93
An organic EL device was prepared as described in Example 92,
except using Compound [IV]-(4) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 700
cd/m.sup.2.
Example 94
An organic EL device was prepared as described in Example 92,
except using Compound [IV]-(5) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 500
cd/m.sup.2.
Example 95
An organic EL device was prepared as described in Example 92,
except using Compound [IV]-(6) as an electron-transporting layer.
Applying 10 V DC to the device generated a luminescence of 400
cd/m.sup.2.
* * * * *